WO1987004321A2 - Use of heterocyclic nitrogen-containing compounds for reducing moisture loss from plants and increasing crop yield - Google Patents

Use of heterocyclic nitrogen-containing compounds for reducing moisture loss from plants and increasing crop yield Download PDF

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Publication number
WO1987004321A2
WO1987004321A2 PCT/US1987/000240 US8700240W WO8704321A2 WO 1987004321 A2 WO1987004321 A2 WO 1987004321A2 US 8700240 W US8700240 W US 8700240W WO 8704321 A2 WO8704321 A2 WO 8704321A2
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alkyl
substituted
unsubstituted
halogen
amino
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PCT/US1987/000240
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French (fr)
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WO1987004321A3 (en
Inventor
David Treadway Manning
James Joseph Cappy
Anson Richard Cooke
Richard Eric Sheads
Tai-Teh Wu
Anihal Lopes
Jennifer Lyn Phillips
Russell James Outcalt
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Rhone-Poulenc Nederlands B.V.
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Application filed by Rhone-Poulenc Nederlands B.V. filed Critical Rhone-Poulenc Nederlands B.V.
Priority to HU871236A priority Critical patent/HUT45848A/en
Priority to BR8705356A priority patent/BR8705356A/en
Publication of WO1987004321A2 publication Critical patent/WO1987004321A2/en
Priority to FI874111A priority patent/FI874111A0/en
Priority to KR870700857A priority patent/KR880700635A/en
Priority to DK496187A priority patent/DK496187A/en
Publication of WO1987004321A3 publication Critical patent/WO1987004321A3/en

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    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N3/00—Preservation of plants or parts thereof, e.g. inhibiting evaporation, improvement of the appearance of leaves or protection against physical influences such as UV radiation using chemical compositions; Grafting wax
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    • C07D253/06—1,2,4-Triazines
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    • C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members with hetero atoms, or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3

Definitions

  • This invention relates to the use of heterocyclic nitrogen-containing compounds for reducing transpirational moisture loss from plants and also for increasing crop yield. This invention further relates to novel heterocyclic nitrogen-containing compounds and processes for the preparation thereof.
  • Transpiration is a well known physiolpgical process involving the passage of water in the form of a vapor through living tissues.
  • the water vapor passes through plant stomatal openings into the atmosphere, thus facilitating the absorption and translocation of aqueous nutrients by plant root systems.
  • the stomatal openings also permit necessary gaseous interchange between plant tissues and the external air. It is believed that only about one percent of the total water absorbed by plant roots is used for plant growth, the remainder being released through plant stomatal openings into the atmosphere by transpiration.
  • transpiration water loss from plants is important for several reasons; in particular, for decreasing requirements for irrigation water especially in dry climate regions, for protecting plants from wilting or other damage during transplantation or shipment or during severe cold weather, and for alleviating water stress in certain types of environments.
  • Water stress as used herein occurs when the transpiration rate exceeds the rate of water uptake by the plant. Water stress appears as a decrease in plant water potential and turgor and can result in wilting or other forms of damage or even plant death.
  • This invention relates to a method for reducing moisture loss from plants which comprises applying to the plant surface an effective amount, sufficient to reduce moisture loss from the plant surface without substantially inhibiting plant photosynthetic electron transport, of a compound having the formula:
  • R 1 , R 2 and X are as defined hereinafter.
  • This invention also relates to a method of increasing crop yield which comprises applying to the crop an effective amount, sufficient to increase crop yield without substantially inhibiting plant photosynthetic electron transport, of a compound having the formula:
  • R 1 , R 2 and X are as defined hereinafter.
  • This invention further relates to novel heterocyclic nitrogen-containing compounds and also to processes for the preparation of said compounds.
  • this invention relates to a method of reducing moisture loss from plants and increasing crop yields by the use of certain heterocyclic nitrogen-containing compounds. More particularly, this invention involves a method for reducing transpirational moisture loss from plants and increasing crop yield which comprises applying to the plant surface or crop an effective amount, sufficient to reduce moisture loss from the plant surface or to increase crop yield without substantially inhibiting plant photosynthetic electron transport, of a compound having the formula:
  • R 1 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents (Z) are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylaIkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl,
  • R 1 is a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents (Z) are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, aIkylcarbonylaIkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkyIsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, diaIky
  • X is a covalent single bond or double bond, a substituted or unsubstituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents (Z) are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbony
  • R 2 is a substituted or unsubstituted, heterocyclic ring system having at least one nitrogen atom which is selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents (Z) are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulf
  • R 3 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents (Z) are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamid
  • -X - R 3 is a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents (Z) are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylamino
  • Y 1 and Y 4 are independently oxygen or sulfur
  • Y 2 and Y 3 are independently oxygen. sulfur, amino or a covalent bond;
  • R 4 and R 5 are independently hydrogen or substituted or unsubstituted alkyl, polyhaloalkyl, phenyl or benzyl in which the permissible substituents (Z) are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, a1
  • alkenyl, haloalkenyl or polyhaloalkenyl alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl,
  • the alkyl-containing moieties above may contain from about 1 to about 100 carbon atoms or greater, preferably from about 1 to about 30 carbon atoms, and more preferably from about 1 to about 20 carbon atoms.
  • the polysaccharide moiety may contain up to about 50 carbon atoms. It is appreciated that all compounds encompassed within formula 1 are compounds having no unfilled bonding positions. It is further appreciated that in order for a substi-tuent to be permissible for the compounds encompassed within formula 1, the valence of the substituent must be appropriate with the bonding capability of the particular carbon atom or heteroatom.
  • B 1 represents a saturated or unsaturated carbon atom and A 1 represents a ring-forming chain of atoms which together with B 1 forms a cyclic system containing from 0 to 4 double bonds or from 0 to 2 triple bonds.
  • a 1 may contain entirely from 2 to 12 carbon atoms, may contain a combination of from 1 to 11 carbon atoms and from 1 to 4 heteroatoms which may be selected independently from N, O, S, P or other heteroatoms, or may contain 4 ring-forming heteroatoms alone.
  • Monocyclic ring systems encompassed by R 2 in formula 1 may include any monocyclic ring system of R 1 and R 3 having at least one nitrogen atom.
  • Ring-forming heteroatoms may in some cases bear oxygen atoms as in aromatic and aliphatic N-oxides and ring systems containing the sulfinyl, sulfonyl, selenoxide and phosphine oxide moieties.
  • Selected carbon atoms contained in cycles formed by B 1 and A 1 containing more than 3 ring-forming atoms may bear carbonyl, thiocarbonyl, substituted or unsubstituted imino groups or substituted or unsubstituted methylidene groups.
  • the group designated as Z represents one or more substituents selected independently from among the group of substituents defined for Z herein.
  • the cycle formed by B 1 and A 1 contains fewer than 4 ring forming members, it should be a saturated carbocycle, i.e. cyclopropyl.
  • the cycle formed by B and A contains fewer than 5 ring-forming members, it should contain no more than 1 heteroatom.
  • Bicyclic ring systems encompassed by R 1 and R 3 in formula 1 may be represented by generalized formulae 3 and 4 as follows:
  • B 2 and B 3 may be independently a saturated or unsaturated carbon atom or a saturated nitrogen atom
  • a 2 and A 3 independently represent the ring-forming chains of atoms described below and Z represents one or more substituents selected independently from among the group of substituents defined for Z herein.
  • Combinations of A 2 and A 3 may contain in combination with B 2 or B 3 from 0 to 5 double bonds.
  • a 2 and A 3 independent of B 2 and B 3 , may contain entirely from 1 to 11 carbon atoms, may contain a combination of 1 to 3 heteroatoms which may be selected independently from among N, O, S, P of other heteroatoms together with from 1 to 10 carbon atoms or may contain from 1-3 ring-forming heteroatoms alone.
  • Ring-forming heteroatoms may in some cases bear oxygen atoms, as in aromatic and aliphatic
  • N-oxides and ring systems containing the sulfinyl, sulfonyl, selenoxide and phosphine oxide groups are N-oxides and ring systems containing the sulfinyl, sulfonyl, selenoxide and phosphine oxide groups.
  • Selected carbon atoms contained in A 2 and A 3 may bear carbonyl, thiocarbonyl, substituted or unsubstituted imino groups or substituted or unsubstituted methylidene groups.
  • Bicyclic ring systems encompassed by R 2 in formula 1 may include any bicyclic ring system of R 1 and R 3 having at least one nitrogen atom.
  • bicyclic ring systems defined for R 1 and R 3 may be spirocyclic ring systems and are not limited to the fused bicyclic structures of formulae 3 and 4.
  • Spirocyclic ring systems may be saturated or unsaturated carbocyclic or- heterocyclic and may be independently substituted by one or more substituents Z as defined herein.
  • Polycyclic ring systems i.e., greater than 2 rings, encompassed by R 1 and R 3 in formula 1 may be represented by generalized formulae 5, 6, 7 and 8 as follows:
  • B 4 , B 5 , B 6 and B 7 may be independently a saturated or unsaturated carbon atom or a saturated nitrogen atom, and A 4 , A 5 , A 6 and A 7 independently represent ring forming chains of atoms which may contain together with one or the other (but not both) of their two associated bridgehead atoms, from 0-2 double bonds.
  • Z represent one or more substituents selected independently from among the group of substituents defined for Z herein.
  • the ring-forming elements of A 4 , A 5 , A 6 and A 7 independent of B 4 , B 5 , B 6 and B 7 may contain from 1-11 carbon atoms, may contain a combination of from 1-10 carbon atoms and from 1-3 heteroatoms which may be selected independently from among N, O, S, P or other heteroatoms, or may contain from 1-3 heteroatoms alone.
  • Ring-forming heteroatoms may in some cases bear oxygen atoms as in aromatic N-oxides and ring systems containing the sulfinyl, sulfonyl, selenoxide and phosphine oxide groups.
  • the group A 6 may at times be defined as a bond.
  • Selected carbon atoms contained in A 4 , A 5 , A 6 and A 7 may bear one or more carbonyl, thiocarbonyl or substituted or unsubstituted imino groups.
  • the groups B 8 , B 9 and B 10 represent independently a saturated or unsaturated carbon atom or a saturated nitrogen atom.
  • the group B 11 may represent a saturated or unsaturated carbon atom or a nitrogen or phosphorous atom.
  • the groups A 8 , A 9 and A 10 represent ring-forming chains of atoms which may contain together with 1 of the groups B 8 , B 9 , B 10 and B 11 from 0-2 double bonds.
  • the ring-forming elements of groups A 8 , A 9 and A 10 independent of groups B 8 , B 9 , B 10 and B 11 may contain from 2-10 carbon atoms, may contain from 1-10 carbon atoms in combination with 1-3 heteroatoms which may be selected independently from among N, O, S, P or other heteroatoms, or may contain from 2-3 heteroatoms alone. Ring-forming heteroatoms may in some cases bear oxygen atoms as in aromatic N-oxides and in ring systems containing the sulfinyl, sulfonyl, selenoxide and phosphine oxide groups. Selected carbon atoms contained in groups A 8 , A 9 and A 10 may bear one or more carbonyl, thiocarbonyl or substituted or unsubstituted imino groups.
  • polycyclic ring systems defined for R 1 and R 3 may be spirocyclic ring systems and are not limited to the fused polycyclic structures of formulae 5, 6, 7 and 8.
  • Spirocyclic ring systems may be saturated or unsaturated, carbocyclic or heterocyclic and may be independently substituted by one or more substituents Z as defined herein.
  • Polycyclic ring systems encompassed by R 2 of formula 1 may include any polycyclic ring system or R 1 and R 3 having at least one nitrogen atom.
  • Illustrative polycyclic ring structures which are encompassed by R 1 and R 3 in formula 1 include the following:
  • Bridged bicyclic structures encompassed by R 1 and R 3 in formula 1 may be represented by generalized formulae 9, 10, and 11 as follows:
  • B 12 and B 13 may be independently a saturated carbon atom optionally substituted by Z or a nitrogen atom, and the groups A 11 , A 12 and A 13 independently represent ring-forming chains of atoms which may contain, independently of B 12 and B 13 , from 0-2 double bonds.
  • the groups Z represent one or more substituents selected independently from among the groups of substituents defined for Z herein.
  • the ring-forming elements of A 11 , A 12 and A 13 may contain entirely from 1-11 carbon atoms, may contain a combination of from 1-10 carbon atoms and from 1-3 heteroatoms which may be selected independently from among N, O, S, P or other heteroatoms, or may contain from 1-3 heteroatoms alone with the proviso that when one of the groups A 11 , A 12 and A 13 is a single heteroatom, the other two groups should contain two or more ring-forming atoms.
  • a second proviso is that when one or both of the groups B 12 and B 13 is nitrogen, the groups A 11 , A 12 and A 13 should contain at least two saturated ring-forming atoms.
  • Ring-forming heteroatoms may in some cases bear oxygen atoms as in the sulfinyl, sulfonyl, selenoxide and phosphine oxide moieties.
  • Selected carbon atoms contained in A 11 , A 12 and A 13 may bear one or more carbonyl, thiocarbonyl or substituted or unsubstituted imino groups.
  • Bridged bicyclic structures encompassed by R 2 of formula 1 may include any bicyclic bridged system of R 1 and R 3 having at least one nitrogen atom.
  • the substituent X may be an unsubstituted heteroatom such as an oxygen or sulfur, as in carbonyl and thiocarbonyl systems, or may be a substituted heteroatom or carbon atom.
  • X may also be a covalent single or double bond.
  • X may further be a saturated or unsaturated, branched or straight chain of carbon atoms; a branched or straight, saturated or unsaturated chain of atoms consisting of both carbon atoms and heteroatoms; or may be a branched or straight, saturated or unsaturated chain consisting entirely of heteroatoms.
  • Selected heteroatomic components of X may bear oxygen atoms as in the case of groups containing the sulfonyl, sulfinyl, N-oxide and phosphine oxide moieties.
  • Selected heteroatomic components of X may bear one or more substituents Z as defined herein.
  • Selected carbon atoms participating in X may bear carbonyl, thiocarbonyl, substituted or unsubstituted imino, substituted or unsubstituted alkylidene or one or more substituents Z as defined herein.
  • R 10 and R 11 are independently hydrogen or substituted or unsubstituted alkyl, polyhaloalkyl, phenyl or benzyl in which the permissible substituents are as defined for Z herein.
  • formula 1 encompasses a wide variety of heterocyclic nitrogen-containing compounds.
  • Illustrative heterocyclic nitrogen-containing compounds within the scope of formula 1 which may be used for reducing transpirational moisture loss from plants and increasing crop yield are included in Tables 1 through 43 below.
  • novel heterocyclic nitrogen-containing compounds of this invention can be depicted by the following formulae:
  • R 24 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl; x 10 represents O, S, SO, SO 2 , NH,
  • Y 19 is the same or different and represents halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl; provided that (i) at least two ring position pairs selected from 2 and 4, 2 and 6, 2 and 3, and 3 and 4 are substituted with the same or different halogen; (ii) when ring positions 2,4 and 6 are substituted with chlorine and j is a value of 0 and X 10 is
  • R 24 is not unsubstituted phenyl
  • R 25 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl
  • X 11 represents O, S, SO, SO 2 , NH,
  • b is a value of 2 to 3;
  • Y 20 is the same or different and represents halogen, alkyl, cyano, polyhaloalkyl, polyhaloalkoxy, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl provided that at least two ring position pairs selected from 2 of Y 20 are halogen;
  • R 26 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl
  • X 12 represents O, S, SO, SO , NH,
  • Y 21 and Y 22 are independently the same or different halogen
  • Y 23 represents hydrogen, halogen, alkyl, polyhaloalkyl, alkoxy, polyhaloalkoxy, cyano, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl;
  • R 27 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl
  • X represents O, S, SO, SO 2 , NH,
  • Y 24 represents halogen
  • Y 25 and Y 26 independently represent hydrogen, halogen, alkyl, polyhaloalkyl, alkoxy, polyhaloalkoxy, cyano, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl provided that at least one of Y 25 and Y 26 is halogen and further provided that when Y 24 , Y 25 and Y 26 are chloro and X 13 is O, then R 27 is not unsubstituted phenyl;
  • R 28 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl
  • X 14 represents O, S, SO, SO 2 , NH,
  • Y 27 and Y 28 are independently halogen
  • Y 29 represents hydrogen, halogen, alkyl, polyhaloalkyl, alkoxy, polyhaloalkoxy, cyano, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl;
  • R 29 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl
  • X 15 represents O, S, SO, SO 2 , NH,
  • Y 30, Y 31 and Y 32 independently represent hydrogen, halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro. acyl or polyhaloalkylsulfonyl provided that at least 2 of
  • Y 30 , Y 31 and Y 32 are halogen
  • R 30 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl
  • X 16 represents O, S, SO, SO 2 , NH,
  • Y 33 , Y 34 and Y 35 independently represent hydrogen, halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl provided that (i) at least 2 of Y 33 , Y 34 and Y 35 are halogen, (ii) when Y 34 and Y 35 are both chloro and X 16 is O, then
  • R 30 is not unsubstituted phenyl, and (iii) when Y 33 and Y 34 are both chloro and X 16 is O, the
  • R 30 is not unsubstituted phenyl or 4-methoxyphenyl
  • d is a value of from 0 to 4 inclusive
  • e is a value of 1 or 2 provided that d and e are not greater than 5;
  • R 31 is the same or different and represents unsubstituted or substituted aryl provided that when R 31 is 2- or 4-aryl then d is not O, aralkyl provided that when R 31 is R-aralkyl then d is not O, alkoxy.
  • cycloalkoxy, aryloxy, aralkoxy provided that when R 31 is 4-aralkoxy then d is not O, arylaryloxy, aralkoxyaralkyl, arylaralkoxy.aryloxyaralkyl, aryloxyalkyl, aryloxyaryloxy, aralkoxyaralkoxy, aryloxyalkoxy, alkylthio, alkenylthio, arylthio, aralkylthio, arylthioaralkyl, arylsulfonylarylsulfonyl, alkylamino, dialkylamino, acyloxy, aroyloxy, alkoxycarbonyloxy, phenylazo provided that X 17 is O or S, naphthylazo, or -OCH 2 O- or -OCH 2 CH 2 O which join adjacent carbon atoms to form a five- or six-membered ring;
  • X 17 represents O, S, NH, CH 2 , -CH 2 O-, -CH 2 S- or -OCH 2 CH 2 O-;
  • Y 37 represents halogen
  • Y 38 represents halogen, alkoxy. alkylthio, alkylsulfonyl, polyhaloalkoxy, polyhaloalkyl, cyano, nitro or unsubstituted or substituted arylthio, aryloxy or arylsulfonyl;
  • f is a value of from 0 to 5;
  • R 32 is the same or different and represents halogen, alkyl, alkenyl, alkynyl, polyhaloalkyl, cyano, nitro, alkylamino, dialkylamino, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, acyl, CO 2 (alkyl), CONH(alkyl), CON(alkyl) 2 , SO 2 N(alkyl) 2 , alkylcarbonyloxy, alfcoxycarbonyloxy, or unsubstituted or substituted aryloxy, arylthio, arylsulfonyl or aroyl;
  • X 18 represents O, S, CH 2 , a single covalent bond or -C ⁇ C-;
  • Y 39 represents halogen, polyhaloalkoxy, polyhaloalkyl. cyano, alkylsulfonyl, alkylsulfonyloxy, polyhaloalkylsulfonyl or polyhaloalkylsulfonyloxy; and Y 40 represents haloalkyl, polyhaloalkyl, alkoxy provided that X 18 is not S or a single covalent bond; polyhaloalkoxy, cyano, alkylthio provided that X 18 is not 0 or a single covalent bond; alkylsulfonyl, nitro, dialkoxyphosphinyl or trialkylammonium;
  • Y 41 is the same or different and represents halogen
  • Y 42 is the same or different and represents halogen, alkoxy, alkylthio or polyhaloalkoxy:
  • Y 52 and Y 53 are independently halogen; g is a value of from 0 to 5 inclusive;
  • X 20 represents -CH(alkyl)O-, -C(alkyl) 2 O-, -OCH 2 -, -CH 2 O-, -CH 2 -, -C(halogen) 2 , -OCH 2 O-, -OCH 2 CH 2 O- or -C ⁇ C- provided that g is a value of at least 1;
  • R 34 represents acyl, alkylsulfonyl, polyhaloalkyl, polyhaloacyl, polyhaloalkylsulfonyl or unsubstituted or substituted aroyl or arylsulfonyl and Y 43 and
  • Y 44 are independently O or S
  • R 35 represents an unsubstituted or substituted heterocyclic ring system selected from isoxazole, isothiazole, pyrazole, imidazole, 1,2,4-triazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4,-thiadiazole, 1,3,4-thiadiazole, oxazole, thiazole, benzopyrazole, benzimidazole, benzoxazole, benzothizole, indole, pyrrole, furan, thiophene, benzofuran, benzothiophene, pyridine, pyrimidine, pyridazine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, quinoline, isoquinoline, quinazoline, phthalazine, benzopyridazine, benzopyrazine, carbazole, dibenzofuran, dibenzothiophene, benzox
  • X 21 represents O, S or NH provided that when X 21 is NH then R 35 is not pyridine, and when X 21 is S then R 35 is not unsubstituted benzothiazole;
  • Y 45 and Y 46 are independently halogen
  • R 37 and R 38 independently represent halogen, nitro, cyano, polyhaloalkyl, polyhaloalkoxy, alkylsulfonyl, polyhaloalkylsulfonyl, acyl, alkoxycarbonyl, polyhaloalkylsulfonyl or R 39 -X 22 - Provided that only one of R 37 and R 38 may be R 39 -X 22 - at any one time;
  • R 39 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl
  • X 22 represents O, S, SO, SO 2 , CH 2 , a single covalent bond, -CH 2 O-, -CH 2 S-,
  • Y 47 represents halogen
  • B 14 represents O, S, NH or N R 40 wherein
  • R 40 represents alkyl, alkylsulfonyl, alkenyl, alkynyl, alkoxycarbonyl; unsubstituted or substituted aryl, aralkyl, aryloxy, arylamino, aroyl or arylsulfonyl; provided that (i) when B 14 is
  • R 39 - , R 39 -alkyl- R 39 -C( O)- ,
  • R 37 and R 38 are other than R 39 - X 22 -; (ii) when B 14 is other than R 39 - , R 39 -alkyl- ,
  • R 41 and R 42 independently represent halogen or R 43 - X 23 - provided that only one of
  • R 41 and R 42 may be R 43 - X 23 - at any one time;
  • R 43 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl
  • X 23 represents O, S, SO, SO 2 , CH 2 , a single covalent bond, -CH 2 O-, CH 2 S-,
  • B 15 represents O, S, NH or N R 44 wherein
  • R 44 represents alkyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkenyl, alkynyl, alkoxycarbonyl; unsubstituted or substituted aryl, aralkyl, aryloxy, arylamino, aroyl or arylsulfonyl; provided that when R 15 is
  • R 41 and R 42 are other than R 43 -X 23 -; and further provided that when B 15 is other than
  • R 45 , R 46 , R 47 , and R 48 independently represent hydrogen, halogen, nitro, cyano, polyhaloalkyl, polyhaloalkoxy, alkylsulfonyl, polyhaloalkylsulfonyl, acyl, alkylthio, alkyl, alkoxy, alkylsulfinyl or R 49 -X 24 - provided that one of R 45 , R 46 , R 47 , and R 48 is
  • R 47 and R 48 include no more than two of hydrogen, alkyl or alkoxy at any one time;
  • R 49 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
  • X represents O, S, SO, SO 2 , CH 2 , a single covalent bond, -CH 2 O-, -CH 2 S-,
  • Y 48 represents halogen
  • B 16 represents O, S or NH
  • R 50 represents an unsubstituted or substituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated;
  • Y 54 and Y 55 are independently halogen
  • R 51 represents or unsubstituted or substituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated;
  • B 19 represents -CH 2 - or -CH(alkyl)-; and i is a value of 0 or 1;
  • Y 56 and Y 57 are independently halogen
  • B 20 represents -CH 2 C(CH 3 ) 4 SCH 2 -
  • -CH 2 CH C(CH 3 )OCH 2 -, -CH 2 CH 2 SCH 2 CH(CH 3 )-,
  • R 52 represents hydrogen, alkenyl; unsubstituted or substituted aryl or alkaryl;
  • Y 58 and Y 59 are independently halogen
  • X 25 represents O, S, NH, CH 2 -CH 2 O- or a single covalent bond
  • R 54 is the same or different and is one or more hydrogen, halogen, alkyl, aryl, aralkyl, alkenyl, alkynyl, polyhaloalkyl, NH 2 , NH(alkyl),
  • N(alkyl) 2 alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, aralkoxy, CO 2 alkyl,
  • X 26 represents O, S, SO, SO 2 , CH 2 , a single covalent bond, -CH 2 O-, -CH 2 S-,
  • Y 50 and Y 51 are the same or different and are halogen
  • R 68 represents unsubstituted or substituted phenyl or 1- or 2-naphthyl
  • X 27 represents -CH(alkyl)O-, -C(alkyl) 2 O-, -OCH 2 -, -C(halogen) 2 , -OCH 2 O-, -OCH 2 CH 2 O-, -CH 2 O-, -C ⁇ C-, -OCH(alkyl)-,
  • R 34 represents acyl, alkylsulfonyl, polyhaloalkyl, polyhaloacyl, polyhaloalkylsulfonyl or unsubstituted or substituted aroyl or arylsulfonyl and Y 43 and
  • Y 44 are independently O or S
  • Z 1 and Z 2 are independently O, S, C 1 -C 8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl: and
  • Y 67 and Y 68 are the same or different and represent hydrogen,halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, aryl, polyhaloalkylsulfonyl, alkylamino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino;
  • R 69 represents unsubstituted or substituted phenyl or 1- or 2-naphthyl
  • X 28 is NH, CH 2 or a covalent bond
  • Z 3 and Z 4 are independently O, S, C 1 -C 8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
  • Y 69 and Y 70 are the same or different and represent hydrogen, halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, aryl, polyhaloalkylsulfonyl, alkylamino, dialkylammo, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino, with the proviso that Y 69 and Y 70 taken together do not represtt eeiitthheerr the same halogen or halogen and hydrogen;
  • R 70 represents an unsubstituted or substituted, unsaturated or saturated, aromatic or non-aromatic heterocyclic ring system selected from isoxazole, isothiazole, pyrazole, imidazole, 1,2,4-triazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4,-thiadiazole, 1,3,4-thiadiazole, oxazole, thiazole, benzopyrazole, benzimidazole, benzoxazole, benzothizole, indole, pyrrole, furan, thiophene, benzofuran, benzothiophene, pyridine, pyrimidine, pyridazine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, quinoline, isoquinoline, quinazoline, phthalazine, benzopyridazine, benzopyrazine, carbazole, dibenzo
  • X 29 represents -CH(alkyl)O-, -C(alkyl) 2 O-, -OCH 2 -, -CH 2 O-, -CH 2 -, a covalent bond, -C(halogen) 2 , -OCH 2 O-,
  • R 34 represents acyl, alkylsulfonyl, polyhaloalkyl, polyhaloacyl, polyhaloalkylsulfonyl or unsubstituted or substituted aroyl or arylsulfonyl and Y 43 and
  • Y 44 are independently O or S;
  • Z 5 and Z 6 are independently O, S, C 1 -C 8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl , aryl, aralkyl , alkenyl or alkynyl ; and
  • Y 71 and Y 72 are the same or different and represent hydrogen, halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, amino, alkylamino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, alkoxycarbonyl, alkylaminocarbonyl, aminocarbonyl, dialkylaminocarbonyl, dialkylaminosulfonyl, alkylaminosulfonyl, .aminosulfonyl, dialkoxyalky
  • R 71 represents unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkadienyl, cycloalkatrienyl, bicycloalkyl, bicycloalkenyl, bicycloalkadienyl, tricycloalkyl, tricycloalkenyl or tricycloalkadienyl:
  • X 30 represents -CH(alkyl)O-, -C(alkyl) 2 O-, -OCH 2 -, -CH 2 O-, -CH 2 -, a covalent bond, -C(halogen) 2 , -OCH 2 O-, -OCH 2 CH 2 O-, -C ⁇ C-, -OCH(alkyl)-, -OC(alkyl) 2 , -OCH(alkyl)O-, -OC(alkyl) 2 O-, -OCH(alkyl)CH 2 O-, -OCH(alkyl)CH(alkyl)O-, -CH(alkyl)CH(alkyl)-, -CH(alkyl)-, -C(alkyl) 2 -, -CH 2 CH 2 O-, -OCH 2 CH 2 -, -CH(alkyl)CH 2 O-, -CH 2 CH 2 -, -CH(CN)O
  • R 34 represents acyl, alkylsulfonyl, polyhaloalkyl, polyhaloacyl, polyhaloalkylsulfonyl or unsubstituted or substituted aroyl or arylsulfonyl and Y 43 and
  • Y 44 are independently O or S;
  • Z 7 and Z 8 are independently O, S, C 1 -C 8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
  • Y 73 and Y 74 are the same or different and represent hydrogen,halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, aryl, polyhaloalkylsulfonyl, alkylamino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy and polyhaloalkylsulfonyloxy;
  • B 21 represents -CH 2 C(CH 3 ) 2 SCH 2 -
  • R 52 represents hydrogen, alkenyl; unsubstituted or substituted aryl or alkaryl; Z 9 and Z 10 are independently O, S, C 1 -C 8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
  • Y 75 and Y 76 are the same or different and represent hydrogen,halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, amino, alkylamino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino;
  • R 72 represents unsubstituted or substituted phenyl or 1- or 2-naphthyl
  • X 31 represents -OCH 2 -, -CH 2 -, a covalent bond, -C(halogen) 2 , -C ⁇ C-, -OCH(alkyl)-,
  • h is a value of from 0 to 2 inclusive
  • Z 11 represents O, S, C 1 -C 8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
  • Y 77 , Y 78 and Y 79 are the same or different and represent hydrogen,halogen, alkyl, hydroxy, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, aIkylamino, amino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino, with the proviso that when Y 77 is halogen and
  • Y 79 is hydrogen then Y 78 cannot be amino, alkylamino, dialkylamino or acylamino and with the further proviso that when Y 77 and Y 78 are the same halogen then Y 79 cannot be hydrogen or hydroxy;
  • R 73 represents an unsubstituted or substituted, unsaturated or saturated, aromatic or non-aromatic heterocyclic ring system selected from isoxazole, isothiazole, pyrazole, imidazole, 1,2,4-triazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4,-thiadiazole, 1,3,4-thiadiazole, oxazole, thiazole, benzopyrazole, benzimidazole, benzoxazole, benzothizole, indole, pyrrole, furan, thiophene, benzofuran, benzothiophene, pyridine, pyrimidine, pyridazine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, quinoline, isoquinoline, quinazo ⁇ ine, phthalazine, benzopyridazine, benzopyrazine, carbazole, di
  • X 32 represents -OCH 2 -, -CH 2 -, a covalent bond, -C(halogen) 2 , -C ⁇ C-, -OCH(alkyl)-, -OC(alkyl) 4 , -CH(alkyl)CH(alkyl)-, -CH(alkyl)-,
  • h is a value of from 0 to 2 inclusive
  • Z 12 represents O, S, C 1 -C 8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
  • Y 80 , Y 81 and Y 82 are the same or different and represent hydrogen,halogen, alkyl, hydroxy, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, alkylamino, amino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino;
  • R 74 represents unsubstituted or substituted alkyl, alkenyl, alkynyl, cyploalkyl cycloalkenyl, cycloalkadienyl, cycloalkatrienyl, bicycloalkyl, bicycloalkenyl, bicycloalkadienyl, tricycloalkyl, tricycloalkenyl or tricycloalkadienyl;
  • X 33 represents -OCH 2 -, -CH 2 -, a covalent bond, -C(halogen) 2 , -C ⁇ C-, -OCH(alkyl)-, -OC(alkyl) 2 , -CH(alkyl)CH(alkyl)-, -CH(alkyl)-,
  • h is a value of from 0 to 2 inclusive
  • Z 13 represents O, S, H 2 -H 2 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl: and Y 83 , Y 84 and Y 85 are the same or different and represent hydrogen, halogen, alkyl, hydroxy, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, alkylamino, amino, dialkylammo, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfon
  • Y 62 , Y 63 , Y 64 , Y 65 and Y 66 are the same or different and are halogen;
  • R 1 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formaraidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhalo
  • R 1 is a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylammocarbonyl, diaIkylaminocarbony
  • X is a covalent single bond or double bond, a substituted or unsubstituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, al
  • R 36 is a substituted or unsubstituted, asymmetrical heterocyclic ring system having at least three nitrogen atoms which are selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxys
  • R 3 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhalo
  • R 3 is a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,
  • Y 1 and Y 4 are independently oxygen or sulfur
  • Y 2 and Y 3 are independently oxygen, sulfur, amino or a covalent bond
  • R 4 and R 5 are independently hydrogen or substituted or unsubstituted alkyl, polyhaloalkyl, phenyl or benzyl in which the permissible substituents are the same or different and are one or moris hydrogen, halogen, alkylcarbonyl , alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylamin
  • the heterocyclic nitrogen-containing compounds encompassed within formula 1 can be prepared by conventional methods known in the art, and many may be available from various suppliers.
  • the novel heterocyclic nitrogen-containing compounds of formulae (i) through (xxxiii) above which may be used in the method of this invention can be prepared by reacting appropriate starting ingredients in accordance with conventional procedures described in the art as illustrated below.
  • novel heterocyclic nitrogen-containing compounds of formula (i) can be prepared by the following general reaction scheme:
  • R 24 , X 10 , a, j and Y 19 are as defined hereinabove.
  • Reactions of this general type for preparing substituted pyridines including process conditions are described for example by Mertel, H.E., The Chemistry of Heterocyclic Compounds, Pyridine and Derivatives-Part Two, Halopyridines, P. 351, Interscience, Wiley, New York (1961). Intermediates such as 2,4,6-trichloropyridine are described in U.S. Patent 3.830,820.
  • other preparation methods for the novel compounds of formula (i) are described in Fuson. R.C., Advanced Organic Chemistry, p. 124, Wiley, New York (1950), and Ochiai, E., Aromatic Amine Oxides, p. 21, Elsevier, New York (1967).
  • novel heterocyclic nitrogen-containing compounds of formula (ii) can be prepared by the following general reaction scheme:
  • R 25 , X 11 , b and Y 20 are as defined hereinabove. Reactions of this general type for preparing substituted pyrazines including process conditions are described for example in U.S. Patent 4.254,125.
  • novel heterocyclic nitrogen-containing compounds of formula (iii) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (v) can be prepared by the following general reaction scheme:
  • R 28 , X 14 , Y 27 , Y 28 and Y 29 are as defined hereinabove.
  • Reactions of this general type for preparing 5-substituted pyrimidines including process conditions and intermediate preparations are described for example by Fieser, L.F. and Fieser, M., Organic Chemistry, p. 310, Heath, Boston (1972) also Brown, D.J., The Pyrimidines; The Chemistry of Heterocyclic Compounds, pp. 50, 166, Interscience, Wiley, New York (1962).
  • the novel heterocyclic .nitrogen-containing compounds of formula (vi) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (vii) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (viii) can be prepared by the following general reaction scheme:
  • 1,3,5-triazines including process conditions and intermediate preparations are described for example in German Patent 952,478, U.S. Patent 2,824,823.
  • R 32 , f, X 18 , Y 39 , Y 40 and Y 49 are as defined hereinabove.
  • Reactions of this general type for preparing substituted 1,3,5-triazines including process conditions and intermediate preparations are described for example in U.S. Patent 3,316,264.
  • Intermediates such as 2,4-dichloro-6-(diethoxyphosphinyl)-1,3,5-triazine are described in Japan Patent 74 46635.
  • Other preparation methods for the novel compounds of formula (ix) are described in Mendoza, C.E. et al., J. Ag. Food Chem., 19, (1), 41-45 (1972).
  • novel heterocyclic nitrogen-containing compounds of formula (x) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (xi) can be prepared by the following general reaction scheme:
  • R 33 , g, X 20 , Y 52 , Y 53 and Y 49 are as defined hereinabove.
  • Reactions of this general type for preparing substituted 1,3,5-triazines including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (viii) above.
  • Other preparation methods for the novel compounds of formula (xi) are described in Allen, C.F.H. and Converse, S., Org. Syn. Coll., Vol. I, 226-227, U.S. Patent 1,911,689, Bessiere-Chretien, Y. and Serne, H., Bull. Soc. Chim. France. (6).
  • novel heterocyclic nitrogen-containing compounds of formula (xii) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (xiii) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (xiv) can be prepared by the following general reaction scheme:
  • R 37 , R 38 , B 14 and Y 47 are as defined hereinabove.
  • Reactions of this general type for preparing substituted azoles including process conditions and intermediate preparations are described in Pahanayak, B.K., J. Ind. Chem. Soc., 55, (3), 264-267 (1978) and Young. T.E. and Amstutz, E.D., J. Amer. Chem. Soc., 73, 4773-4775. (1951).
  • Other preparation methods for the novel compounds of formula (xiv) are described by Tripathi, H. et al., Agric. Biol. Chem., 37, 1375 (1973) and Young, T.E. and Amstutz, E.D., J. Amer. Chem. Soc. 73, 4773-4775 (1951).
  • novel heterocyclic nitrogen-containing compounds of formula (xv) can be prepared by the following general reaction scheme:
  • R 41 , R 42 , and B 15 are as defined hereinabove.
  • Reactions of this general type for preparing substituted 1,2,4-azoles including process conditions and intermediate preparations are described by Selim, M. and Selim, M. , Bull. Soc. Chim. France. 1219-1220 (1967).
  • novel heterocyclic nitrogen-containing compounds of formula (xvi) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (xvii) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (xviii) can be prepared by the following general reaction scheme:
  • R 50 , B 17 , Y 54 , Y 55 and Y 49 are as defined hereinabove.
  • Reactions of this general type for preparing substituted 1,3,5-triazines including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (viii) above.
  • Other preparation methods for the novel compounds of formula (xix) are described by Beech, W.F., J. Chem. Soc., (C), 466-472 (1967).
  • novel heterocyclic nitrogen-containing compounds of formula (xx) can be prepared by the following general reaction scheme:
  • 1,3,5-triazines including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (viii) above.
  • novel heterocyclic nitrogen-containing compounds of formula (xxi) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (xxii) can be prepared by "the following general reaction scheme:
  • R 53 , X 25 , Y 60 , Y 61 and Y 49 are as defined hereinabove. Reactions of this general type for preparing substituted 1,3,5-triazines including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (viii) above.
  • novel heterocyclic nitrogen-containing compounds of formula (xxiii) can be prepared by the following general reaction scheme:
  • R 54 , X 26 , Y 50 and Y 51 are as defined hereinabove. Reactions of this general type for preparing hexahydro-1,3,5-triazines including process conditions are described for example by
  • novel heterocyclic nitrogen-containing compounds of formula (xxiv) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (xxvi) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (xxvii) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (xxviii) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (xxix) can be prepared by the following general reaction scheme:
  • Suitable halogenating agents include, for example, PCL 5 , POCl 3 , PBr 5 and POBr 3 and mixtures thereof.
  • Reactions of this general type for preparing substituted pyridazinones including process conditions and intermediate preparations are described for example in Yuki Gosei Kagaku Kyotai Shi 28, (4), 462-463 (1970).
  • Other preparation methods for the novel compounds of formula (xxix) are described in Yakugaku Zasshi 86, (12), 1168-1172 (1966), Acta Dol. Pharm.
  • novel heterocyclic nitrogen-containing compounds of formula (xxx) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (xxxi) can be prepared by the following general reaction scheme:
  • R 74 , X 33 , Z 13 , Y 83 , Y 84 AND Y 85 are as defined hereinabove. Reactions of this general type for preparing substituted pyridazinones including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (xxix) above.
  • novel heterocyclic nitrogen-containing compounds of formula (xxxii) can be prepared by the following general reaction scheme:
  • novel heterocyclic nitrogen-containing compounds of formula (xxxiii) can be prepared by the following general reaction scheme:
  • the antitranspirant compounds of formula 1 have been found to significantly reduce plant and crop usage of water, i.e., reduce transpiration rate, and increase the resistance of plant leaf surfaces to the loss of moisture vapor, i.e., increase diffusive resistance.
  • the antitranspirant compounds used in this invention are substantially non-inhibiting of photosynthetic light-requiring reactions, substantially non-phytotoxic to growing plants and serve to increase crop yields in comparison with untreated crops at similar conditions, especially in regions where plants are subject to moisture stress conditions.
  • the antitranspirant compounds used in this invention provide for the conservation of soil moisture by reducing plant and crop usage of water during certain development periods, e.g., vegetative period, thereby making the unused water available at other periods of plant or crop development, e.g., reproductive growth period.
  • stomata are minute openings in the epidermis of plant leaf surfaces through which occurs gaseous interchange between the atmosphere and the intercellular spaces within the leaf. It is believed that the antitranspirant compounds of formula 1 effectively reduce the transpiration rate in plants by closing plant stomata or constricting plant stomatal openings to such a degree that moisture loss is reduced and, in addition, the compounds exhibit substantially no detrimental effect on photosynthetic electron flow.
  • the photosynthetic process in plants consists of light-requiring reactions, i.e., light reactions, and non-light-requiring reactions, i.e., dark reactions.
  • the dark reactions in general involve a complex of enzyme-mediated reactions which provide for the conversion of carbon dioxide to sugar.
  • Photosystem I and Photosystem II Two light-requiring reactions are involved in plant photosynthesis and are conventionally termed Photosystem I and Photosystem II. See. for example, Salisbury. F.B. and Ross, C.W., Plant Physiology, pp. 131-135 (1978). These photosystems are interconnected by an electron transport chain, and provide reducing power and chemical energy to the dark reactions. Inhibition of either or both of these photosystems can detrimentally affect photosynthesis, thereby causing plant injury or even plant death.
  • the antitranspirant compounds used in this invention have been found to cause no or substantially no inhibition of Photosystem I or Photosystem II.
  • the herbicide atrazine is known to substantially inhibit the light reactions of photosynthesis, particularly the electron transport chain. See, for example, Jachetta, J.J. and Radosevich, S.R., Weed Science 29: 37-43 (1981).
  • Such herbicidal inhibition leads to a buildup of carbon dioxide within the leaf which causes closure of the stomates.
  • the antitranspirant activity of atrazine is associated with its herbicidal properties.
  • substantially no inhibition of photosynthetic electron transport refers to no or little inhibition of photosynthetic electron transport.
  • an effective amount of a heterocyclic nitrogen-containing compound for reducing moisture loss from plants refers to an antitranspirationally effective amount of the compound sufficient to reduce transpirational moisture loss from plants without substantially inhibiting plant photosynthetic electron transport.
  • an effective amount of a heterocyclic nitrogen-containing compound for increasing crop yield refers to a yield enhancing effective amount of the compound sufficient to increase crop yield without sustantially inhibiting plant photosynthetic electron transport.
  • the effective amount of compound can vary over a wide range depending on the particular compound employed, the particular crop to be treated, environmental and climatic conditions, and the like, provided that the amount of compound used does not cause substantial inhibition of plant photosynthetic electron transport or substantial phytotoxicity, e.g., foliar burn, chlorosis or necrosis, to the plant.
  • the compound can preferably be applied to plants and crops at a concentration of from about 0.25 to 15 pounds of compound per acre as more fully described below.
  • heterocyclic nitrogen-containing compounds contemplated by formula 1 may be employed according to a variety of conventional methods known to those skilled in the art.
  • Compositions containing the compounds as the active ingredient will usually comprise a carrier and/or diluent, either liquid or solid.
  • Suitable liquid diluents or carriers include water, petroleum distillates, or other liquid carriers with or without surface active agents.
  • Liquid concentrates may be prepared by dissolving one of these compounds with a nonphytotoxic solvent such as acetone, xylene, nitrobenzene, cyclohexanone or dimethylformamide and dispersing the active ingredients in water with the aid of suitable surface active emulsifying and dispersing agents.
  • dispersing and emulsifying agents are dictated by the nature of the composition and the ability of the agent to facilitate the dispersion of the active ingredient. Generally, it is desirable to use as little of the agent as is possible, consistent with the desired dispersion of the active ingredient in the spray so that rain does not re-emulsify the active ingredient after it is applied to the plant and wash it off the plant.
  • Nonionic, anionic. or cationic dispersing and emulsifying agents may be employed, for example, the condensation products of alkylene oxides with phenol and organic acids, alkyl aryl sulfonates, complex ether alcohols, quaternary ammonium compounds, and the like.
  • the active ingredient is dispersed in and on an appropriately divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fuller's earth, and the like.
  • an appropriately divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fuller's earth, and the like.
  • the aforementioned dispersing agents as well as lignosulfonates can be included.
  • the required amount of the active ingredient contemplated herein may be applied per acre treated in from 1 to 200 gallons or more of liquid carrier and/or diluent or in from about 5 to 500 pounds of inert solid carrier and/or diluent.
  • concentration in the liquid concentrate will usually vary from about 5 to 95 percent by weight and in the solid formulations from about 0.5 to about 90 percent by weight.
  • Satisfactory sprays or dusts for general use contain from about 0.1 to about 100 pounds of active ingredient per acre, preferably from about 0.25 to about 15 pounds of active ingredient per acre, and more preferably from about 0.5 to about 5 pounds of active ingredient per acre.
  • Formulations useful in the conduct of this invention can also contain other optional ingredients such as stabilizers or other biologically active compounds, insofar as they do not impair or reduce the activity of the active ingredient and do not harm the plant being treated.
  • Other biologically active compounds include, for example, one or more insecticidal, herbicidal, fungicidal, nematicidal, miticidal, plant growth regulators or other known compounds. Such combinations may be used for the known or other purpose of each ingredient and may provide a synergistic effect.
  • the antitranspirant compounds of formula l. are preferably applied to plants and crops under substantially little or no water stress conditions, or what can be considered as average or normal growing conditions.
  • a preferred condition for compound application is prior to substantial soil moisture loss. While not wishing to be bound to any particular theory, it is believed that application of the antitranspirant compounds does not result in a reduction of the minimum total water requirements of a treated plant or crop, but rather the application of such compounds serves to promote more efficient water utilization by treated plants and crops.
  • the antitranspirant effect does not reduce the total amount of water needed to grow a given plant or crop except for water savings which may be realized for some crops under irrigation, but rather such antitranspirant effect is manifested by an increase in yield of treated crops having no or limited irrigation and rainfall in comparison with untreated crops at similar conditions.
  • the antitranspirant compounds of formula 1 are preferably applied to plants and crops under conditions which favor large gradients in water vapor pressure between the saturated atmosphere within the leaf and the atmosphere around the leaf. Such conditions include low atmospheric humidity, high light/heat loads on the leaf, and high rates of air movement.
  • the application of the antitranspirant compounds of formula 1 to plants reduces the amount of water utilized by the plane for on the order of about a 1 to 6 week period and therefore provides for a greater amount of reserve water available in the soil during other developmental periods such as the critical reproductive growth phase.
  • This soil moisture conservation can minimize any water deficit within plant tissues during critical developmental periods such as the reproductive growth phase resulting in increased crop yield.
  • the antitranspirant compounds used in this invention may likewise be applied during the plant reproductive growth phase to obtain similar results.
  • the antitranspirant compounds of formula 1 are useful for decreasing irrigation water requirements especially in dry climate regions, for protecting plants from wilting or other damage during transplantation or shipment or during severe cold weather, and for alleviating water stress in certain types of environments as indicated above.
  • Such compounds are useful in agriculture, horticulture and related fields and can be applied to vegetation such as non-deciduous ornamental shrubs, evergreens, trees, and the like, to protect them against winter kill.
  • a chief cause of winter kill is an excessive loss of moisture from leaf surfaces on sunny or windy days when the ground is frozen and the root systems cannot replace the water loss.
  • the antitranspirant compounds can also be applied to other ornamentals such as roses and other flowers, Christmas trees, and the like, to preserve freshness and retard needle drop.
  • the antitranspirant compounds can further be used in avoiding or minimizing the effects of summer scald and transplant shock.
  • antitranspirant compounds of formula 1 may also be used to control foliar diseases on crops such as wheat and oats. See, for example, Avant Gardener, Vol. 18, No. 1, November, 1985, in which antitranspirants are used to control fungus diseases.
  • plants refer in general to any agronomic or horticultural crops, ornamentals and turfgrasses.
  • Illustrative of plants which may be treated by the antitranspirant compounds of formula 1 according to the method of this invention include, for example, corn, cotton, sweet potatoes, white potatoes, alfalfa, wheat, rye, upland rice, barley, oats, sorghum, dry beans, soybeans, sugar beets, sunflowers, tobacco, tomatoes, canola, deciduous fruit, citrus fruit, tea, coffee, olives, pineapple, cocoa, banana, sugar cane, oil palm, herbaceous bedding plants, woody shrubs, turfgrasses, ornamental plants, evergreens, trees, flowers, and the like.
  • crops refer in general to any of the illustrative agronomic or horticultural crops above.
  • Transplanted stock refers in general to tobacco, tomatoes, eggplant, cucumbers, lettuce, strawberries, herbaceous bedding plants, woody shrubs, tree seedlings and the like.
  • the antitranspirant compounds contemplated herein reduce transpirational moisture loss from plants and increase crop yields.
  • Such compounds have a high margin of safety in that when used in sufficient amount to provide an antitranspirant effect or yield enhancing effect, they do not inhibit plant photosynthetic electron transport or burn or injure, the plant, and they resist weathering which includes wash-off caused by rain, decomposition by ultraviolet light, oxidation, or hydrolysis in the presence of moisture or, at least, such decomposition, oxidation, and hydrolysis as would materially decrease the desirable antitranspirant characteristic of the active ingredient or impart undesirable characteristics, for instance, phytotoxicity, to the active ingredients.
  • Mixtures of the active compounds may be employed if desired as well as combinations of the active compounds with other biologically active compounds or ingredients as indicated above.
  • Compound 48 This compound is referred to hereinafter as Compound 48.
  • Example VIII In a manner similar to Example VIII, 4.63 grams (0.04 mole) of 2-chloroaniline and 6.69 grams (0.04 mole) of cyanuric chloride were reacted in the presence of 3.89 grams (0.04 mole) of 2,6-lutidine except that the cooling bath was removed at the end of the feed period and the stirred mixture allowed to warm to room temperature. After filtering off lutidine hydrochloride, the filtrate was freed of acetone solvent under reduced pressure and the resulting solid was crystallized from a mixture of hexane and benzene.
  • This compound is referred to hereinafter as Compound 66.
  • Example XIV Into a solution containing 600 milligrams (0.002 mole) of 4,6-dichloro-2-(4'-nitrophenylamino)-1,3,5-triazine prepared in Example XIV in 300 milliliters of CH 2 Cl 2 was bubbled HBr gas at room temperature for a period of 4 hours. The resulting mixture was stored in a refrigerator for about 48 hours and an oil, which separated from CH 2 Cl 2 , was collected by decantation.
  • This compound is referred to hereinafter as Compound 67.
  • This compound is referred to hereinafter as Compound 68.
  • Compound 70 This compound is referred to hereinafter as Compound 70.
  • This compound is referred to hereinafter as Compound 71.
  • This compound is referred to hereinafter as Compound 73.
  • Part B Preparation of 2,4-dichloro-6- (4'-sec-butyloxyphenoxy)-1,3,5-triazine Into a 100 mill iliter 3-necked round bottom f lask equipped with a thermometer, addition funnel and nitrogen inlet was added cyanuric chloride (2.22 grams, 0.01 mole) dissolved in 20 milliliters of acetone. After cooling to a temperature of 0-5oC, 4-(sec-butyloxy) phenol (2.0 grams, 0.01 mole) prepared in Part A and 2,6-lutidine (1.40 milliliters, 0.01 mole) dissolved in 20 milliliters of acetone were slowly added dropwise via the addition funnel.
  • the temperature of the reaction was maintained between 0-5oC during the addition.
  • the reaction mixture was then stirred at room temperature for a period of 16 hours. After this period, the reaction mixture was filtered through a Celite pad and the pad rinsed with acetone. Ice-water was added and the oil which precipitated was extracted with EtOAc. The EtOAc layers were washed with water, dried (MgSO 4 ) and cpncentrated to give a brown semi-solid.
  • This compound is referred to hereinafter as Compound 74.
  • Example XXIV Into a solution containing 2.0 grams (0.007 mole) of 4-chloro-6-methyl-2-(2',4'-dichlorophenoxy)-1,3,5-triazine prepared in Example XXIV in 300 milliliters of CH 2 Cl 2 was bubbled dry HBr gas for a period of 3 hours. The mixture was allowed to stand at room temperature for about 18 hours. The suspension was then filtered and the solids partitioned between NaHCO solution and CH 2 Cl 2 .
  • This compound is referred to hereinafter as Compound 88.
  • Example XXVIII The column chromatography fractions from Example XXVIII were examined and a group identified as containing 4-chloro-6-(2',2',2'-trifluoroethoxy)-2-phenyl-1,3,5-triazine as a second component. These were combined and purified by preparative liquid chromatography (silica gel) using 10% ethyl acetate in hexane as the eluent to give 320 milligrams (0.001 mole) of 4-chloro-6-(2',2',2'-trifluoroethoxy)-2-phenyl-1,3,5-triazine as an oil. Elemental analysis of the product indicated the following:
  • Compound 90 This compound is referred to hereinafter as Compound 90.
  • This compound is referred to hereinafter as Compound 92.
  • Example XXXII In a manner similar to that employed in Example XXXII, other compounds were prepared.
  • reaction mixture was then diluted with 150 milliliters of water and extracted with CH 2 Cl 2
  • 2,4-Dichlorobenzaldehyde oxime prepared in Part A was reacted with cyanuric chloride using a procedure similar to that described in Example XXXII above.
  • the reaction mixture was filtered to remove the precipitate and the filtrate was poured onto ice causing a yellow solid to form.
  • the solid was separated and recrystallized from acetone-water to yield 2.1 grams (0.006 mole) of 2,4-dichlorobenzaldehyde O-(4, 6-dichloro-1,3,5-triazin- 2-yl)oxime as pale yellow needles having a melting point of 124°C-124.5°C. Elemental analysis of the product indicated the following:
  • This compound is referred to hereinafter as Compound 96.
  • the compound is referred to hereinafter as Compound 97.
  • This compound is referred to hereinafter as Compound 98.

Abstract

A method for reducing transpirational moisture loss from plants and increasing crop yield by applying to the plant surface or crop an effective amount of a heterocyclic nitrogen-containing compound. This invention also relates to novel heterocyclic nitrogen-containing compounds and processes for the preparation thereof.

Description

Use of Heterocyclic Nitrogen-Containing
Compounds for Reducing Moisture Loss from
Plants and Increasing Crop Yield
Brief Summary of the Invention
Technical Field
This invention relates to the use of heterocyclic nitrogen-containing compounds for reducing transpirational moisture loss from plants and also for increasing crop yield. This invention further relates to novel heterocyclic nitrogen-containing compounds and processes for the preparation thereof.
Background of the Invention
Transpiration is a well known physiolpgical process involving the passage of water in the form of a vapor through living tissues. In plant transpiration, the water vapor passes through plant stomatal openings into the atmosphere, thus facilitating the absorption and translocation of aqueous nutrients by plant root systems. The stomatal openings also permit necessary gaseous interchange between plant tissues and the external air. It is believed that only about one percent of the total water absorbed by plant roots is used for plant growth, the remainder being released through plant stomatal openings into the atmosphere by transpiration.
It has been determined that only a very low rate of transpiration in plants is required for necessary nutrient transport and normal plant growth. Although complete cessation of transpiration would most probably be detrimental or even fatal to plants, it is believed that a decrease in plant transpiration rate up to about 40 to 50 percent would not be detrimental to plants. See, for example, U.S. Patent No. 4,094,845.
The reduction of transpiration water loss from plants is important for several reasons; in particular, for decreasing requirements for irrigation water especially in dry climate regions, for protecting plants from wilting or other damage during transplantation or shipment or during severe cold weather, and for alleviating water stress in certain types of environments. Water stress as used herein occurs when the transpiration rate exceeds the rate of water uptake by the plant. Water stress appears as a decrease in plant water potential and turgor and can result in wilting or other forms of damage or even plant death.
Various methods have been developed for decreasing transpirational moisture loss from plants. Such methods are described, for example, in U.S. Patent Nos. 4,094,845, 4,397,681, 3,890,158, 3,847,641, 3,826,671, 3,676,102, 3,539,373, 3,339,990. 3.199.944. and also EP 73,760-B. Various materials described in the patent literature which have been used to reduce water loss from plants by transpiration include, for example, carboxylated hydrophilic acrylic polymers, wax emulsions, animal tallow, alkenyl succinic acids, long chain esters of lower organic acids, polyisocyanates, liquid polyterpenes, benzyl alkyl ammonium salts, and the like. However, even though these materials may decrease transpirational moisture loss from plants, many of these materials have a detrimental effect on other plant processes such as photosynthesis, respiration, cell division, and the like.
The use of 2-chloro-4-ethylamino-6-isopropylamino-s-triazine (atrazine) for reducing transpirational water loss from plants has also been reported in the literature. See, for example. G. D. Wills et al., Weeds 11: 253-255 (1963) and also James C. Graham et al., Weed Science 16: 389-392 (1968). However, inhibition of plant photosynthetic light-requiring reactions, e.g., photosynthetic electron transport, and plant phytotoxicity are associated with the use of atrazine as an antitranspirant compound.
Accordingly, it is an object of this invention to provide a method for the use of certain heterocyclic nitrogen-containing compounds to reduce transpirational moisture loss from plants, and thereby provide for more efficient soil moisture utilization. It is another object of this invention to provide a method for the use of certain heterocyclic nitrogen-containing compounds to increase crop yields. It is yet another object of this invention to provide novel heterocyclic nitrogen-containing compounds and processes for the preparation thereof. These and other objects will readily become apparent to those skilled in the art in light of the teachings herein set forth. Disclosure of the Invention
This invention relates to a method for reducing moisture loss from plants which comprises applying to the plant surface an effective amount, sufficient to reduce moisture loss from the plant surface without substantially inhibiting plant photosynthetic electron transport, of a compound having the formula:
R1 - X - R2
wherein R1, R2 and X are as defined hereinafter.
This invention also relates to a method of increasing crop yield which comprises applying to the crop an effective amount, sufficient to increase crop yield without substantially inhibiting plant photosynthetic electron transport, of a compound having the formula:
R1 - X - R2
wherein R1, R2 and X are as defined hereinafter.
This invention further relates to novel heterocyclic nitrogen-containing compounds and also to processes for the preparation of said compounds.
Detailed Description As indicated above, this invention relates to a method of reducing moisture loss from plants and increasing crop yields by the use of certain heterocyclic nitrogen-containing compounds. More particularly, this invention involves a method for reducing transpirational moisture loss from plants and increasing crop yield which comprises applying to the plant surface or crop an effective amount, sufficient to reduce moisture loss from the plant surface or to increase crop yield without substantially inhibiting plant photosynthetic electron transport, of a compound having the formula:
R1 - X - R2
wherein:
R1 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents (Z) are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylaIkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, diaIkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylarainothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkox/sulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium, -X, = X, -X = R3, = X-R3,
Figure imgf000009_0001
or
; or
Figure imgf000009_0002
R1 is a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents (Z) are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, aIkylcarbonylaIkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkyIsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, diaIkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, aIkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium. arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium, -X, = X, -X = R3, = X-R3,
Figure imgf000012_0001
or
Figure imgf000012_0002
X is a covalent single bond or double bond, a substituted or unsubstituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents (Z) are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3
Figure imgf000014_0001
or
and
Figure imgf000014_0002
R2 is a substituted or unsubstituted, heterocyclic ring system having at least one nitrogen atom which is selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents (Z) are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, aIkylaminothiocarbonyl, diaIkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, aIkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, araIkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 = X-R3,
-X - R3 ,
Figure imgf000017_0002
or
Figure imgf000017_0001
Figure imgf000017_0003
wherein: R3 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents (Z) are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiόcarbonyl, alkylaminothiocarbonyl, diaIkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000019_0001
Figure imgf000019_0002
or or
Figure imgf000019_0003
R3 is a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents (Z) are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl. alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, aIkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl) amino, araIkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 , = X-R3 ,
-X - R3
Figure imgf000021_0001
Figure imgf000021_0002
or
Figure imgf000022_0001
Y1 and Y4 are independently oxygen or sulfur;
Y2 and Y3 are independently oxygen. sulfur, amino or a covalent bond; and
R4 and R5 are independently hydrogen or substituted or unsubstituted alkyl, polyhaloalkyl, phenyl or benzyl in which the permissible substituents (Z) are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, a1kylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl. alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carhoxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyioxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino. aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 , = X-R3,
-X - R3 ,
Figure imgf000024_0001
or
Figure imgf000024_0002
The alkyl-containing moieties above may contain from about 1 to about 100 carbon atoms or greater, preferably from about 1 to about 30 carbon atoms, and more preferably from about 1 to about 20 carbon atoms. The polysaccharide moiety may contain up to about 50 carbon atoms. It is appreciated that all compounds encompassed within formula 1 are compounds having no unfilled bonding positions. It is further appreciated that in order for a substi-tuent to be permissible for the compounds encompassed within formula 1, the valence of the substituent must be appropriate with the bonding capability of the particular carbon atom or heteroatom.
Monocyclic ring systems encompassed by R1 and R3 in formula 1 may be represented by generalized formula 2 as follows:
Figure imgf000025_0001
wherein B1 represents a saturated or unsaturated carbon atom and A1 represents a ring-forming chain of atoms which together with B1 forms a cyclic system containing from 0 to 4 double bonds or from 0 to 2 triple bonds. A1 may contain entirely from 2 to 12 carbon atoms, may contain a combination of from 1 to 11 carbon atoms and from 1 to 4 heteroatoms which may be selected independently from N, O, S, P or other heteroatoms, or may contain 4 ring-forming heteroatoms alone.
Monocyclic ring systems encompassed by R2 in formula 1 may include any monocyclic ring system of R1 and R3 having at least one nitrogen atom.
Ring-forming heteroatoms may in some cases bear oxygen atoms as in aromatic and aliphatic N-oxides and ring systems containing the sulfinyl, sulfonyl, selenoxide and phosphine oxide moieties.
Selected carbon atoms contained in cycles formed by B1 and A1 containing more than 3 ring-forming atoms may bear carbonyl, thiocarbonyl, substituted or unsubstituted imino groups or substituted or unsubstituted methylidene groups.
The group designated as Z represents one or more substituents selected independently from among the group of substituents defined for Z herein. When the cycle formed by B1 and A1 contains fewer than 4 ring forming members, it should be a saturated carbocycle, i.e. cyclopropyl. When the cycle formed by B and A contains fewer than 5 ring-forming members, it should contain no more than 1 heteroatom.
Illustrative monocyclic ring structures which are encompassed by R1 and R3 in formula l include the following:
Figure imgf000026_0001
Figure imgf000026_0002
Figure imgf000027_0001
Figure imgf000027_0002
Figure imgf000027_0003
Figure imgf000027_0004
Figure imgf000027_0005
Figure imgf000028_0001
wherein Z is as defined herein.
Bicyclic ring systems encompassed by R1 and R3 in formula 1 may be represented by generalized formulae 3 and 4 as follows:
Figure imgf000028_0002
wherein B2 and B3 may be independently a saturated or unsaturated carbon atom or a saturated nitrogen atom, A2 and A3 independently represent the ring-forming chains of atoms described below and Z represents one or more substituents selected independently from among the group of substituents defined for Z herein. Combinations of A2 and A3 may contain in combination with B2 or B3 from 0 to 5 double bonds. A2 and A3, independent of B2 and B3, may contain entirely from 1 to 11 carbon atoms, may contain a combination of 1 to 3 heteroatoms which may be selected independently from among N, O, S, P of other heteroatoms together with from 1 to 10 carbon atoms or may contain from 1-3 ring-forming heteroatoms alone.
Ring-forming heteroatoms may in some cases bear oxygen atoms, as in aromatic and aliphatic
N-oxides and ring systems containing the sulfinyl, sulfonyl, selenoxide and phosphine oxide groups.
Selected carbon atoms contained in A2 and A3 may bear carbonyl, thiocarbonyl, substituted or unsubstituted imino groups or substituted or unsubstituted methylidene groups.
Bicyclic ring systems encompassed by R2 in formula 1 may include any bicyclic ring system of R1 and R3 having at least one nitrogen atom.
In regard to structures encompassed within formulae 3 and 4, it is noted as follows:
(a) When B2 and B3 are both nitrogen. the groups A2 and A3 should each contain no fewer than three ring atoms;
(b) When B2 but not B3 is nitrogen, either of A2 or A3 should contain at least three ring atoms and the other at least two ring atoms;
(c) When either of groups A2 or A3 contains fewer than three ring atoms, the other should contain at least three ring atoms and the bridgehead atoms should be saturated; (d) When the group A2 or A3 contains a carbon atom bearing a carbonyl, thiocarbonyl, imino or methylidene group, it should together with B2 and B3 form a cycle having at least four members;
(e) When an annular double bond is exocyclic to either of the two rings represented in structures 3 and 4, it should be contained in a ring containing at least five members and be exocyclic to a ring containing at least five members; and
(f) When a group A2 or A3 is joined to the bridgehead atoms B2 and B3 by 2 double bonds, the group A2 or A3 is understood to contain one double bond and the bridgehead atoms are considered to be unsaturated.
It is recognized that bicyclic ring systems defined for R1 and R3 may be spirocyclic ring systems and are not limited to the fused bicyclic structures of formulae 3 and 4. Spirocyclic ring systems may be saturated or unsaturated carbocyclic or- heterocyclic and may be independently substituted by one or more substituents Z as defined herein.
Illustrative bicyclic ring structures which are encompassed by R1 and R3 in formula 1 included the following:
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000031_0002
Figure imgf000031_0003
Figure imgf000031_0004
Figure imgf000032_0001
Figure imgf000032_0002
Figure imgf000032_0003
Figure imgf000032_0004
Figure imgf000033_0001
Figure imgf000033_0002
Figure imgf000033_0003
Figure imgf000033_0004
Figure imgf000033_0005
Figure imgf000034_0001
Polycyclic ring systems, i.e., greater than 2 rings, encompassed by R1 and R3 in formula 1 may be represented by generalized formulae 5, 6, 7 and 8 as follows:
Figure imgf000034_0002
Figure imgf000034_0003
Figure imgf000034_0004
Figure imgf000034_0005
wherein B4 , B5, B6 and B7 may be independently a saturated or unsaturated carbon atom or a saturated nitrogen atom, and A4, A5, A6 and A7 independently represent ring forming chains of atoms which may contain together with one or the other (but not both) of their two associated bridgehead atoms, from 0-2 double bonds. The groups
Z represent one or more substituents selected independently from among the group of substituents defined for Z herein.
The ring-forming elements of A4 , A5, A6 and A7 independent of B4 , B5, B6 and B7 may contain from 1-11 carbon atoms, may contain a combination of from 1-10 carbon atoms and from 1-3 heteroatoms which may be selected independently from among N, O, S, P or other heteroatoms, or may contain from 1-3 heteroatoms alone. Ring-forming heteroatoms may in some cases bear oxygen atoms as in aromatic N-oxides and ring systems containing the sulfinyl, sulfonyl, selenoxide and phosphine oxide groups. The group A6 may at times be defined as a bond. Selected carbon atoms contained in A4, A5, A6 and A7 may bear one or more carbonyl, thiocarbonyl or substituted or unsubstituted imino groups.
On structure 8 the groups B8 , B9 and B10 represent independently a saturated or unsaturated carbon atom or a saturated nitrogen atom. The group B11 may represent a saturated or unsaturated carbon atom or a nitrogen or phosphorous atom. The groups A8, A9 and A10 represent ring-forming chains of atoms which may contain together with 1 of the groups B8, B9, B10 and B11 from 0-2 double bonds.
The ring-forming elements of groups A8, A9 and A10 independent of groups B8, B9, B10 and B11 may contain from 2-10 carbon atoms, may contain from 1-10 carbon atoms in combination with 1-3 heteroatoms which may be selected independently from among N, O, S, P or other heteroatoms, or may contain from 2-3 heteroatoms alone. Ring-forming heteroatoms may in some cases bear oxygen atoms as in aromatic N-oxides and in ring systems containing the sulfinyl, sulfonyl, selenoxide and phosphine oxide groups. Selected carbon atoms contained in groups A8, A9 and A10 may bear one or more carbonyl, thiocarbonyl or substituted or unsubstituted imino groups.
It is recognized that polycyclic ring systems defined for R1 and R3 may be spirocyclic ring systems and are not limited to the fused polycyclic structures of formulae 5, 6, 7 and 8. Spirocyclic ring systems may be saturated or unsaturated, carbocyclic or heterocyclic and may be independently substituted by one or more substituents Z as defined herein.
Polycyclic ring systems encompassed by R2 of formula 1 may include any polycyclic ring system or R1 and R3 having at least one nitrogen atom.
Illustrative polycyclic ring structures which are encompassed by R1 and R3 in formula 1 include the following:
Figure imgf000037_0001
Figure imgf000037_0002
Figure imgf000037_0003
Figure imgf000038_0001
Figure imgf000038_0002
Figure imgf000038_0003
Figure imgf000038_0004
Figure imgf000039_0001
Bridged bicyclic structures encompassed by R1 and R3 in formula 1 may be represented by generalized formulae 9, 10, and 11 as follows:
Figure imgf000039_0002
Figure imgf000039_0003
Figure imgf000039_0004
wherein B12 and B13 may be independently a saturated carbon atom optionally substituted by Z or a nitrogen atom, and the groups A11, A12 and A13 independently represent ring-forming chains of atoms which may contain, independently of B12 and B13, from 0-2 double bonds. The groups Z represent one or more substituents selected independently from among the groups of substituents defined for Z herein. The ring-forming elements of A11, A12 and A13, independent of B12 and B13, may contain entirely from 1-11 carbon atoms, may contain a combination of from 1-10 carbon atoms and from 1-3 heteroatoms which may be selected independently from among N, O, S, P or other heteroatoms, or may contain from 1-3 heteroatoms alone with the proviso that when one of the groups A11, A12 and A13 is a single heteroatom, the other two groups should contain two or more ring-forming atoms. A second proviso is that when one or both of the groups B12 and B13 is nitrogen, the groups A11, A12 and A13 should contain at least two saturated ring-forming atoms.
Ring-forming heteroatoms may in some cases bear oxygen atoms as in the sulfinyl, sulfonyl, selenoxide and phosphine oxide moieties. Selected carbon atoms contained in A11, A12 and A13 may bear one or more carbonyl, thiocarbonyl or substituted or unsubstituted imino groups.
Bridged bicyclic structures encompassed by R2 of formula 1 may include any bicyclic bridged system of R1 and R3 having at least one nitrogen atom.
Illustrative bridged bicyclic structures which are encompassed by R1 and R3 in formula 1 include the following:
Figure imgf000041_0001
Figure imgf000041_0002
Figure imgf000041_0003
Figure imgf000041_0004
Figure imgf000041_0005
Figure imgf000042_0001
Figure imgf000042_0002
Figure imgf000042_0003
Figure imgf000042_0004
Figure imgf000043_0001
Figure imgf000043_0002
Figure imgf000043_0003
Figure imgf000043_0004
The substituent X may be an unsubstituted heteroatom such as an oxygen or sulfur, as in carbonyl and thiocarbonyl systems, or may be a substituted heteroatom or carbon atom. X may also be a covalent single or double bond. X may further be a saturated or unsaturated, branched or straight chain of carbon atoms; a branched or straight, saturated or unsaturated chain of atoms consisting of both carbon atoms and heteroatoms; or may be a branched or straight, saturated or unsaturated chain consisting entirely of heteroatoms. Selected heteroatomic components of X may bear oxygen atoms as in the case of groups containing the sulfonyl, sulfinyl, N-oxide and phosphine oxide moieties. Selected heteroatomic components of X may bear one or more substituents Z as defined herein. Selected carbon atoms participating in X may bear carbonyl, thiocarbonyl, substituted or unsubstituted imino, substituted or unsubstituted alkylidene or one or more substituents Z as defined herein.
Illustrative structures which are encompassed by substituent X include the following:
Figure imgf000044_0001
Figure imgf000044_0002
Figure imgf000044_0003
Figure imgf000044_0004
Figure imgf000045_0001
Figure imgf000045_0002
Figure imgf000045_0004
Figure imgf000045_0003
Figure imgf000045_0007
Figure imgf000045_0005
Figure imgf000045_0006
Figure imgf000045_0008
Figure imgf000045_0009
Figure imgf000045_0010
Figure imgf000046_0001
wherein m is a value of from 0 to 8, n is a value of from 0 to 2, and R8, R9. R10 and R11 are independently hydrogen or substituted or unsubstituted alkyl, polyhaloalkyl, phenyl or benzyl in which the permissible substituents are as defined for Z herein.
It is readily apparent that formula 1 encompasses a wide variety of heterocyclic nitrogen-containing compounds. Illustrative heterocyclic nitrogen-containing compounds within the scope of formula 1 which may be used for reducing transpirational moisture loss from plants and increasing crop yield are included in Tables 1 through 43 below.
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000106_0001
Figure imgf000107_0001
Figure imgf000108_0001
Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000121_0001
Figure imgf000122_0001
Figure imgf000123_0001
Figure imgf000124_0001
Figure imgf000125_0001
Figure imgf000126_0001
Figure imgf000127_0001
Figure imgf000128_0001
Figure imgf000129_0001
Figure imgf000130_0001
Figure imgf000131_0001
Figure imgf000132_0001
Figure imgf000134_0001
Figure imgf000135_0001
Figure imgf000136_0001
Figure imgf000137_0001
Figure imgf000138_0001
Figure imgf000139_0001
Figure imgf000140_0001
Figure imgf000141_0001
Figure imgf000142_0001
Figure imgf000143_0001
Figure imgf000144_0001
Figure imgf000145_0001
Figure imgf000146_0001
Figure imgf000147_0001
Figure imgf000148_0001
Figure imgf000149_0001
Figure imgf000150_0001
Figure imgf000151_0001
Figure imgf000152_0001
Figure imgf000153_0001
Figure imgf000154_0001
Figure imgf000155_0001
Figure imgf000156_0001
Figure imgf000157_0001
Figure imgf000158_0001
Figure imgf000159_0001
Figure imgf000160_0001
Figure imgf000161_0001
Figure imgf000162_0001
Figure imgf000163_0001
Figure imgf000164_0001
Figure imgf000165_0001
Figure imgf000166_0001
Figure imgf000167_0001
Figure imgf000168_0001
Figure imgf000169_0001
Figure imgf000170_0001
Figure imgf000171_0001
Figure imgf000172_0001
Figure imgf000173_0001
Figure imgf000174_0001
Figure imgf000175_0001
Figure imgf000176_0001
Figure imgf000177_0001
Figure imgf000178_0001
Figure imgf000179_0001
Figure imgf000180_0001
Figure imgf000181_0001
Figure imgf000182_0001
Figure imgf000183_0001
Figure imgf000184_0001
Figure imgf000185_0001
Figure imgf000186_0001
Figure imgf000187_0001
Figure imgf000188_0001
Figure imgf000189_0001
Figure imgf000190_0001
Figure imgf000192_0001
Figure imgf000193_0001
Figure imgf000194_0001
Figure imgf000195_0001
Figure imgf000196_0001
Figure imgf000197_0001
Figure imgf000198_0001
Figure imgf000199_0001
Figure imgf000200_0001
Figure imgf000201_0001
Figure imgf000202_0001
Figure imgf000203_0001
Figure imgf000204_0001
Figure imgf000205_0001
Figure imgf000206_0001
Figure imgf000207_0001
Figure imgf000208_0001
Figure imgf000209_0001
Figure imgf000210_0001
Figure imgf000211_0001
Figure imgf000212_0001
Figure imgf000213_0001
Figure imgf000214_0001
Figure imgf000215_0001
Figure imgf000216_0001
Figure imgf000217_0001
Figure imgf000218_0001
Figure imgf000219_0001
Figure imgf000220_0001
Figure imgf000221_0001
Figure imgf000222_0001
Figure imgf000223_0001
Figure imgf000224_0001
Figure imgf000225_0001
Figure imgf000226_0001
Figure imgf000227_0001
Figure imgf000228_0001
Figure imgf000229_0001
Figure imgf000230_0001
Figure imgf000231_0001
Figure imgf000232_0001
Figure imgf000233_0001
Figure imgf000234_0001
Figure imgf000235_0001
Figure imgf000236_0001
Figure imgf000237_0001
Figure imgf000238_0001
Figure imgf000239_0001
It is appreciated that the particular coiαpounds listed in Tables 1 through 43 hereinabove are illustrative of heterocyclic nitrogen-containing compounds which may be used in reducing transpirational water loss from plants and increasing crop yields according to this invention. This invention is not to be construed as being limited only to the use of these compounds; but rather, this invention includes those heterocyclic nitrogen-containing compounds encompassed- within formula 1 hereinabove.
The novel heterocyclic nitrogen-containing compounds of this invention can be depicted by the following formulae:
wherein:
Figure imgf000240_0001
R24 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl; x10 represents O, S, SO, SO2, NH,
-C H2O4-, -C H2S-, -CH C H3)O-, -CH(CN)O-,
-CH=NO-, -C(C H3)=NO-, -CH2CH2O-, -CH2CH2-,
-C≡C-. -CH2SO-, -CH2SO2-, -OCH2CH2O-.
-CH(alkyl)-, cr -CONH-; j is a value of 0 or 1; a is a value of from 2 to 4 inclusive; and
Y19 is the same or different and represents halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl; provided that (i) at least two ring position pairs selected from 2 and 4, 2 and 6, 2 and 3, and 3 and 4 are substituted with the same or different halogen; (ii) when ring positions 2,4 and 6 are substituted with chlorine and j is a value of 0 and X10 is
SO2 then R24 is not unsubstituted phenyl; and
(iii) when ring positions 2,3, and 5 are substituted with chlorine and j is a value of l and X10 is S, then R24 is not unsubstituted phenyl.
Figure imgf000241_0001
wherein:
R25 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X11 represents O, S, SO, SO2, NH,
C H2, a single covalent bond, -CHOO-, -C H2S-,
-CH(C H3)O-, -CH(CN)O-, -CH=NO-, -C(C H3)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO2-, -OCH2CH2O-, -CH(alkyl)-, or -CONH-; b is a value of 2 to 3; and
Y20 is the same or different and represents halogen, alkyl, cyano, polyhaloalkyl, polyhaloalkoxy, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl provided that at least two ring position pairs selected from 2 of Y20 are halogen;
Figure imgf000242_0001
wherein:
R 26 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X12 represents O, S, SO, SO , NH,
C H2, a single covalent bond, -C H2O-, -C H2S-,
-CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(C H3)=NO-,
-CH2CH2O-, -CH2CH2-, -CSC-, -CH2SO-,
-CH2SO2-, -OCH2CH2O-, -CH(alkyl)-, or -CONH-;
Y21 and Y22 are independently the same or different halogen; and
Y23 represents hydrogen, halogen, alkyl, polyhaloalkyl, alkoxy, polyhaloalkoxy, cyano, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl;
Figure imgf000242_0002
wherein:
R27 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X represents O, S, SO, SO2, NH,
C H2, a single covalent bond, -CH2O-, -CH2S-,
-CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO2-, -OCH2CH2O-, -CH(alkyl)-, or -CONH-;
Y24 represents halogen; and Y25 and Y26 independently represent hydrogen, halogen, alkyl, polyhaloalkyl, alkoxy, polyhaloalkoxy, cyano, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl provided that at least one of Y25 and Y26 is halogen and further provided that when Y24, Y25 and Y26 are chloro and X13 is O, then R27 is not unsubstituted phenyl;
Figure imgf000243_0001
wherein:
R28 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X14 represents O, S, SO, SO2, NH,
CH2, a single covalent bond, -CH2O-, -CH2S-,
-CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO -, -OC H2CH2O-, -CH(alkyl)-, or -CONH-;
Y27 and Y28 are independently halogen; and
Y29 represents hydrogen, halogen, alkyl, polyhaloalkyl, alkoxy, polyhaloalkoxy, cyano, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl;
Figure imgf000243_0002
wherein:
R29 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X15 represents O, S, SO, SO2, NH,
CH2, a single covalent bond, -CH2O-, -CH2S-,
-CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3) =NO-,
-CH2CH2O-. -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO2-, -OCH2CH2O-, -CH(alkyl)-, or
-CONH-; and
Y30, Y31 and Y32 independently represent hydrogen, halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro. acyl or polyhaloalkylsulfonyl provided that at least 2 of
Y30, Y31 and Y32 are halogen;
wherein:
Figure imgf000244_0001
R30 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X16 represents O, S, SO, SO2, NH,
CH2, a single covalent bond, -CH2O-, -CH2S-,
-CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO- ,
-CH2SO2-, -OCH2CH2O-, -CH(alkyl)-, or
-CONH-; and
Y33, Y34 and Y35 independently represent hydrogen, halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl provided that (i) at least 2 of Y33, Y34 and Y35 are halogen, (ii) when Y34 and Y35 are both chloro and X16 is O, then
R30 is not unsubstituted phenyl, and (iii) when Y33 and Y34 are both chloro and X16 is O, the
R30 is not unsubstituted phenyl or 4-methoxyphenyl;
wherein:
Figure imgf000245_0001
d is a value of from 0 to 4 inclusive; e is a value of 1 or 2 provided that d and e are not greater than 5;
R31 is the same or different and represents unsubstituted or substituted aryl provided that when R31 is 2- or 4-aryl then d is not O, aralkyl provided that when R31 is R-aralkyl then d is not O, alkoxy. cycloalkoxy, aryloxy, aralkoxy provided that when R31 is 4-aralkoxy then d is not O, arylaryloxy, aralkoxyaralkyl, arylaralkoxy.aryloxyaralkyl, aryloxyalkyl, aryloxyaryloxy, aralkoxyaralkoxy, aryloxyalkoxy, alkylthio, alkenylthio, arylthio, aralkylthio, arylthioaralkyl, arylsulfonylarylsulfonyl, alkylamino, dialkylamino, acyloxy, aroyloxy, alkoxycarbonyloxy, phenylazo provided that X17 is O or S, naphthylazo, or -OCH2O- or -OCH2CH2O which join adjacent carbon atoms to form a five- or six-membered ring;
Y36 is the same or different and represents halogen, alkyl, alkenyl, alkynyl, -CH=CHCH=CH-, which joins adjacent carbon atoms to form a six-membered ring, -(CH2)4, nitro, cyano, haloalkyl, or polyhaloalkyl;
X17 represents O, S, NH, CH2, -CH2O-, -CH2S- or -OCH2CH2O-;
Y37 represents halogen; and
Y38 represents halogen, alkoxy. alkylthio, alkylsulfonyl, polyhaloalkoxy, polyhaloalkyl, cyano, nitro or unsubstituted or substituted arylthio, aryloxy or arylsulfonyl;
Figure imgf000246_0001
wherein: f is a value of from 0 to 5;
R32 is the same or different and represents halogen, alkyl, alkenyl, alkynyl, polyhaloalkyl, cyano, nitro, alkylamino, dialkylamino, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, acyl, CO2 (alkyl), CONH(alkyl), CON(alkyl)2, SO2N(alkyl)2, alkylcarbonyloxy, alfcoxycarbonyloxy, or unsubstituted or substituted aryloxy, arylthio, arylsulfonyl or aroyl;
X18 represents O, S, CH2 , a single covalent bond or -C≡C-;
Y39 represents halogen, polyhaloalkoxy, polyhaloalkyl. cyano, alkylsulfonyl, alkylsulfonyloxy, polyhaloalkylsulfonyl or polyhaloalkylsulfonyloxy; and Y40 represents haloalkyl, polyhaloalkyl, alkoxy provided that X18 is not S or a single covalent bond; polyhaloalkoxy, cyano, alkylthio provided that X18 is not 0 or a single covalent bond; alkylsulfonyl, nitro, dialkoxyphosphinyl or trialkylammonium;
Figure imgf000247_0001
wherein:
Y41 is the same or different and represents halogen;
Y42 is the same or different and represents halogen, alkoxy, alkylthio or polyhaloalkoxy: and
X19 represents 0, dithio, -P(=O)(O-alkyl)-, -P(alkyl)-, -P(O-alkyl)-, sulfinyl. sulfonyl, thiosulfinyl, a single covalent bond, carbonyl, aminocarbonylamino, aminooxalylamino, aminocarbonylalkylenecarbonylamino, aminoalkyleneamino, unsubstituted or substituted oxyaryloxy provided that 1,3-arylenebis (oxy) is substituted with at least one εubstitutent, oxyaryl- alkylaryloxy, oxyarylthioaryloxy, oxyarylsulfonylaryloxy and oxyarylaryloxy;
Figure imgf000247_0002
wherein:
Y 52 and Y53 are independently halogen; g is a value of from 0 to 5 inclusive;
R33 is the same or different and represents halogen, alkyl, alkenyl, alkynyl, polyhaloalkyl, cyano, nitro, amino, alkylamino, dialkylamino, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkoxycarbonyl, alkylaminocarbonyl, aminocarbonyl, dialkylaminocarbonyl, dialkylaminosulfonyl, aϊkylaminosulfonyl, .aminosulfonyl, alkylcarbonyl, dialkoxyalkyl, alkylcarbonyloxy, alkylcarbonylalkylamino, -CH=CHCH=CH- which joins adjacent carbon atoms to form a six-membered ring, or unsubstituted or substituted aryl, aralkyl, aryloxy, arylthio, arylsulfonyl or aralkoxy; and
X20 represents -CH(alkyl)O-, -C(alkyl)2O-, -OCH2-, -CH2O-, -CH2-, -C(halogen)2, -OCH2O-, -OCH2CH2O- or -C≡C- provided that g is a value of at least 1;
-OCH(alkyl)-, -OC(alkyl) , -OCH(alkyl)O-,
-OC(alkyl)2O-, -OCH(aϊkyl)CH2O-,
-OCH(alkyl)CH(alkyl)O-, -CH(alkyl)CH(alkyl)-,
-CH(alkyl)-, -C(alkyl)2-, -CH2CH2O-,
-OCH2CH2-, -CH(alkyl)CH2O-, -CH2CH2-,
-CH(CN)O-, -C(alkyl)(CN)O-, -CH(polyhaloalkyl)O-, -C(CN)=NO-, -C(NH alkyl)=NO-, -C[N(alkyl)2]=NO-, -C(S-alkyl)=NO-, -C(O-alkyl)=NO-, -SC(=O)O-, -NHC(=O)O-, -N(alkyl)C(=O)O-, SO, SO2, -CH2S(O)h-, -CH(alkyl)S(O)h-, -S(O)hCH2-, -OC(=S)S-, -C(=O)S-, -C(=S)-S-, -NH(alkyl)C(=O)S-, -O(C=O)S-, -N(R34)-, -SO2NH-, -SO N(alkyl)-,
-CONH-, -CON(alkyl)-, -SC(=O)N(alkyl)-, -S-C(=O)NH-,
-NHSO2NH-, -N(alkyl)SO2N(alkyl)-,
-N(alkyl)SO2NH-, -NHSO2N(alkyl)-,
-C(O-alkyl)=N-, -C(S-alkyl)=N-, -CH(halogen)-,
-C(alkyl) (halogen), -CH(CN)-, -C(alkyl) (CN)-,
-NH(alkyl)NH-, -NH-N(alkyl)-; -NH-NH- or -N=N- provided that R33 is not nitro; -C(=O)-,
-C(=O)C(=O)-, -CH(O-alkyl)-, -CH2C(-O)-,
-C(=O)CH2, -CH(alkyl)C(=O)-, -C(=O)CH(alkyl)-,
-CH=CH-, -C(alkyl)=CH-, -CH=C(alkyl)-,
-C(alkyl)=C(alkyl)-, -C(=O)CH=CH-,
-P(Y43)(Y44-alkyl)-, unsubstituted or substituted -P(Y43) (Y44-aryl) or arylene, -Si(halogen)2-, -Si(alkyl)2, -OC(=O)N(alkyl)-,
-OCH2C(=O)N(alkyl)-, -N(alkyl)CON(alkyl)-;
-OC(=O)NH-, -NHCONH-, -SO2NHC(=O)NH-, or
-NHC(=S)NH provided that g is a value of at least 1;
Figure imgf000249_0002
wherein h is a value of from 0 to 2 inclusive, R 34 represents acyl, alkylsulfonyl, polyhaloalkyl, polyhaloacyl, polyhaloalkylsulfonyl or unsubstituted or substituted aroyl or arylsulfonyl and Y43 and
Y44 are independently O or S;
Figure imgf000249_0001
wherein:
R35 represents an unsubstituted or substituted heterocyclic ring system selected from isoxazole, isothiazole, pyrazole, imidazole, 1,2,4-triazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4,-thiadiazole, 1,3,4-thiadiazole, oxazole, thiazole, benzopyrazole, benzimidazole, benzoxazole, benzothizole, indole, pyrrole, furan, thiophene, benzofuran, benzothiophene, pyridine, pyrimidine, pyridazine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, quinoline, isoquinoline, quinazoline, phthalazine, benzopyridazine, benzopyrazine, carbazole, dibenzofuran, dibenzothiophene, benzoxazine, phthalimide, benzopyran, dibenzopyridine, pyridopyridine, pyrazolopyrimidine, tetrahydropyrimidinedione, coumarin, piperidine, morpholine, tetrahydrofuran, tetrahydrothiophene, pyrrolidine, thiomorpholine, piperidine-2-one, piperidine-2, 6-dione, 2,5-pyrrolidinedione, 3-morpholinone, 2-oxohexamethyleneimine, 2-oxotetramethyleneimine, 1-pyrazoline, 2-pyrazoline, pyrazolidine, 2-imidazolidinone, 2-imidazolidinethione, 2,4-imidazolidinedione, 1,2-oxathiolane, 1,3-oxathiolane, 1,3-oxathiane, 1,4-oxathiane, 2(1H)-pyrazinone, 2H-pyran-2-one, 4H-pyran-4-one, 2H-pyran-2-thione, 4H-pyran-4-thione, tetrahydropyran, tetrahydrothiopyran, 7-oxabicyclo[2,2,1]heptane,
7-azabicyclo[2,2,1]heptane, oxetane, coumarin, 1,3-dioxane, 1,4-dioxane or 1,3-dioxolane; X21 represents O, S or NH provided that when X21 is NH then R35 is not pyridine, and when X21 is S then R35 is not unsubstituted benzothiazole; and
Y45 and Y46 are independently halogen;
Figure imgf000251_0001
or
Figure imgf000251_0002
wherein:
R37 and R38 independently represent halogen, nitro, cyano, polyhaloalkyl, polyhaloalkoxy, alkylsulfonyl, polyhaloalkylsulfonyl, acyl, alkoxycarbonyl, polyhaloalkylsulfonyl or R39-X22- Provided that only one of R37 and R38 may be R39-X22- at any one time;
R39 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X22 represents O, S, SO, SO2, CH2, a single covalent bond, -CH2O-, -CH2S-,
-CH(CH2)O-, -CH(CN)O-, -CH=NO-, -C(CH2)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO2-, -OCH2CH2O-, -CH(alkyl)-, or -CONH-;
Y47 represents halogen; and
B14 represents O, S, NH or N R40 wherein
R40 represents alkyl, alkylsulfonyl, alkenyl, alkynyl, alkoxycarbonyl; unsubstituted or substituted aryl, aralkyl, aryloxy, arylamino, aroyl or arylsulfonyl; provided that
Figure imgf000252_0003
(i) when B14 is
R39-
Figure imgf000252_0004
, R39-alkyl-
Figure imgf000252_0005
R39-C(=O)-
Figure imgf000252_0006
,
R39-SO2
Figure imgf000252_0009
, R39-O-
Figure imgf000252_0008
or R39-NH-
Figure imgf000252_0007
, then both
R37 and R38 are other than R39- X22-; (ii) when B14 is other than R39-
Figure imgf000252_0013
, R39-alkyl-
Figure imgf000252_0015
,
R39-C(=O)-
Figure imgf000252_0010
, R39-SO2
Figure imgf000252_0011
, R39-O-
Figure imgf000252_0012
R39-NH-
Figure imgf000252_0014
, then one of R37 and R38 is
R39- X22-; and (iii) when R38 and Y47 are both chlorine and X22 is a single covalent bond in formula (xiii), then R39 is not unsubstituted phenyl;
or
Figure imgf000252_0001
Figure imgf000252_0002
wherein:
R41 and R42 independently represent halogen or R43- X23- provided that only one of
R41 and R42 may be R43- X23- at any one time;
R43 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X23 represents O, S, SO, SO2, CH2, a single covalent bond, -CH2O-, CH2S-,
-CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO2-, -OCH2CH2O-, -CH(alkyl)-, -CONH- ; and
B15 represents O, S, NH or N R44 wherein
R44 represents alkyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkenyl, alkynyl, alkoxycarbonyl; unsubstituted or substituted aryl, aralkyl, aryloxy, arylamino, aroyl or arylsulfonyl; provided that when R15 is
R43-
Figure imgf000253_0003
, R43-alkyl-
Figure imgf000253_0004
, R43-C(=O)-
Figure imgf000253_0005
R43-SO2
Figure imgf000253_0006
, R43-O-
Figure imgf000253_0007
or R43-NH-
Figure imgf000253_0008
, then both
R41 and R42 are other than R43-X23-; and further provided that when B15 is other than
R43-
Figure imgf000253_0009
, R43-alkyl-
Figure imgf000253_0010
R43-C(=O)-
Figure imgf000253_0011
,
R43-SO2
Figure imgf000253_0012
, R43-O-
Figure imgf000253_0013
or R43-NH-
Figure imgf000253_0014
then one of
R41 and R42 iS R43-X23-;
or
Figure imgf000253_0002
Figure imgf000253_0001
wherein:
R 45, R46, R47, and R48 independently represent hydrogen, halogen, nitro, cyano, polyhaloalkyl, polyhaloalkoxy, alkylsulfonyl, polyhaloalkylsulfonyl, acyl, alkylthio, alkyl, alkoxy, alkylsulfinyl or R49-X24- provided that one of R45, R46, R47, and R48 is
R49- X29- and further provided that R45, R46,
R47 and R48 include no more than two of hydrogen, alkyl or alkoxy at any one time;
R49 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl; X represents O, S, SO, SO2, CH2, a single covalent bond, -CH2O-, -CH2S-,
-CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO2-, -OCH2CH2O-, -CH(alkyl)-, -CONH-;
Y48 represents halogen; and
B16 represents O, S or NH;
Figure imgf000254_0001
wherein:
R50 represents an unsubstituted or substituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated;
B17 represents -CH=N-, -N=CH-, -CH=CH-,
-CO-, -SO2-, -CH2CO-, -COCH2-, -CONH-, -NHCO-,
-SO2NH-, -NHSO2-, -SO2N(alkyl)-,
-N(alkyl)SO2-, -OSO2-, -CS-,
Figure imgf000255_0002
, -NH-,
-N(alkyl)-, -OCH2, -SCH2-, -NHCH2-,
-N(alkyl)CH2-, -SCO-, -OCH2-, -OCO-, -CH2-, -CH2CH2- or -SCH2CO-; provided that when B17 is -CO- and R50 is phenyl, then the phenyl is substituted; and
Y54 and Y55 are independently halogen;
Figure imgf000255_0001
wherein:
R51 represents or unsubstituted or substituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated;
R38 represents -CH=N-, -N=CH-, -CH=CH-,
-CO-, -SO2-, -CH2CO-, -COCH2-, -CONH-, -NHCO-,
-SO2NH-, -NHSO2-, -SO2N(alkyl)-,
-N(alkyl)SO2-, -OSO2-, -CS-,
Figure imgf000256_0002
,
-NH-,-N(alkyl)-, -OCH2, -SCH2-, -NHCH2-,
-N(alkyl)CH2, -S-CO-, -OCH2-, -OCO-, -CH2-,
-CH2CH2- or -SCH2CO-;
B19 represents -CH2- or -CH(alkyl)-; and i is a value of 0 or 1; and
Y56 and Y57 are independently halogen;
Figure imgf000256_0001
wherein:
B20 represents -CH2C(CH3)4SCH2-,
-CH2CH=C(CH3)OCH2-, -CH2CH2SCH2CH(CH3)-,
-CH2CH2SCH2CH2-, -CH2SCH2CO-,
-COCH2C(CH3)2CH2CO- ,
-COCH2CH(C6H5)CH2CO-,
-CONH(C6H5)CH2CH2O-, -COC(CH3)2NHCO-,
-CH2CH2N(C6H5)CH2CH2-,
-CH2N(C6H5)CH2CH2-,
-CH2CH2CH(C6H5)CH2CH2-, -CO(CH2)3CO-,
-CO(CH2)2CO-, -COCH2CH(CH3)CH2CO-,
-COCH(CH2)CH2CO-, -COC(CH3)2CH2CO-,
-COC(CH3)4C(CH3)2CO-, -CO(CH2)4CO-, -CO(CH2)5CO-, -CO(CH2)5CH2-,
-CO(CH2)4CH2-, -CO(CH2)3CH2-,
-CO(CH2)2CH2-, -COCH2SCH2CO-,
-COCH2N(R52)CH2CO-, -COCH2OCH2CO-,
-COCH2SCS-, -COCH=CH-N=CH-,
-CH2CH(C6H5)CH,-N=CH-, or -CO2-CH2CH2-;
R52 represents hydrogen, alkenyl; unsubstituted or substituted aryl or alkaryl; and
Y58 and Y59 are independently halogen;
Figure imgf000257_0001
wherein:
R53 represents unsubstituted or substituted cycloalkenyl, cycloalkadienyl, cycloalkatrienyl, bicycloalkyl, bicycloalkadienyl, triτycloalkyl, bicycloalkenyl, tricycloalkenyl or tricycloalkadienyl in which the permissible substituents are the same or different and are one or more alkyl, halogen, haloalkyl, polyhaloalkyl, alkoxy, alkylthio, alkylsulfonyl, polyhaloalkoxy, nitro, cyano, acyl, aroyl, aryl, alkoxycarbonyl, alkoxycarbonyloxy, acyloxy, oxo, or -CH=CHCH=CH- or -CH=CHCH2- which join adjacent carbon atoms to form a βix-or five membered ring; Y60 and Y61 are independently halogen; and
X25 represents O, S, NH, CH2 -CH2O- or a single covalent bond;
Figure imgf000258_0001
wherein:
R54 is the same or different and is one or more hydrogen, halogen, alkyl, aryl, aralkyl, alkenyl, alkynyl, polyhaloalkyl, NH2, NH(alkyl),
N(alkyl)2, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, aralkoxy, CO2alkyl,
CONH(alkyl), CONH2, CON(alkyl)2,
SO2N(alkyl)2, SO2NH(alkyl), SO2NH2, acyl,
CO(O-alkyl)2, acyloxy, acyl-CON(alkyl) or
2,3-(-CH=CHCH=CH-), 3,4-(-CH=CHCH=CH-),
2,3-(CH2)4- or 3,4-(CH2)4- which join the adjacent carbon atoms to form and unsubstituted or substituted six-membered ring;
X26 represents O, S, SO, SO2, CH2, a single covalent bond, -CH2O-, -CH2S-,
-CH(CH3)O, -CH(CN)O-, -CH=NO-, -C(CH2)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO2-, -OCH2CH2O-, -OCH2CH2- or
-OCH2-; and
Y50 and Y51 are the same or different and are halogen;
Figure imgf000259_0001
R68 represents unsubstituted or substituted phenyl or 1- or 2-naphthyl;
X27 represents -CH(alkyl)O-, -C(alkyl)2O-, -OCH2-, -C(halogen)2, -OCH2O-, -OCH2CH2O-, -CH2O-, -C≡C-, -OCH(alkyl)-,
-OC(alkyl)2, -OCH(alkyl)O-, -OC(alkyl)2O-,
-OCH(alkyl)CH2O-, -OCH(alkyl)CH(alkyl)O-,
-CH(alkyl)CH(alkyl)-, -CH(alkyl)-, -C(alkyl)2-,
-CH2CH2O-, -OCH2CH2-, -CH(alkyl)CH2O-,
-CH2CH2-, -CH(CN)O-, -C(alkyl)(CN)O-,
-CH(polyhaloalkyl)O-, -C(CN)=NO-, -C(NH alkyl)=NO-,
-C[N(alkyl) ]=NO-, -C(S-alkyl)=NO-,
-C(O-alkyl)=NO-, -SC(=O)O-, -NHC(=O)O-,
-N(alkyl)C(=O)O-, SO, SO2, -CH2S(O)H-,
-CH(alkyl)S(O)h-, -S(O)hCH2-, -OC(=S)S-,
-C(=O)S-, -C(=S)-S-, -NH(alkyl)C(=O)S-, -O(C=O)S-, -N(alkyl)-, -N( R34)-,-SO2NH-, -SO2N(alkyl)-, -CONH-, -CON(alkyl)-, -SC(=O)N(alkyl)-, -S-C(=O)NH-, -NHSO2NH-, -N(alkyl)SO2N(alkyl)-, -N(aIkyl) SO2NH-, -NHSO2N(alkyl)-, -C(O-alkyl)=N-, -C(S-alkyl)=N-, -CH(halogen)-, -C(alkyl) (halogen)-, -CH(CN)-, -C(alkyl) (CN)-, -NH(alkyl)NH-, -NH-N(alkyl)-; -NH-NH-, -N=N-, -C(=O)-, -C(-O)C(=O)-, -CH(O-alkyl)-, -CH2C(=O)-, -C(=O)CH2, -CH(alkyl)C(=O)-, -C(=O)CH(alkyl)-, -CH=CH-, -C(alkyl)=CH-, -CH=C(alkyl)-, -C(alkyl)=C(alkyl)-, -C(=O)CH=CH-, -P( Y43)( Y44-alkyl)-, unsubstituted or substituted -P( Y43) ( Y44-aryl) or arylene,
-Si(halogen)2-, -Si(alkyl)2, -OC(=O)N(alkyl)-, -OCH2C(=O)N(alkyl)-, -N(alkyl)CON(alkyl)-; -OC(=O)NH-, -NHCONH-, -SO2NHC(=O)NH-, -NHC(=S)NH,
Figure imgf000260_0002
wherein h is a value of from 0 to 2 inclusive, R34 represents acyl, alkylsulfonyl, polyhaloalkyl, polyhaloacyl, polyhaloalkylsulfonyl or unsubstituted or substituted aroyl or arylsulfonyl and Y43 and
Y44 are independently O or S;
Z1 and Z2 are independently O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl: and
Y67 and Y68 are the same or different and represent hydrogen,halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, aryl, polyhaloalkylsulfonyl, alkylamino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino;
Figure imgf000260_0001
R69 represents unsubstituted or substituted phenyl or 1- or 2-naphthyl;
X28 is NH, CH2 or a covalent bond; Z3 and Z4 are independently O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y69 and Y70 are the same or different and represent hydrogen, halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, aryl, polyhaloalkylsulfonyl, alkylamino, dialkylammo, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino, with the proviso that Y69 and Y70 taken together do not represemntt eeiitthheerr the same halogen or halogen and hydrogen;
Figure imgf000261_0001
R70 represents an unsubstituted or substituted, unsaturated or saturated, aromatic or non-aromatic heterocyclic ring system selected from isoxazole, isothiazole, pyrazole, imidazole, 1,2,4-triazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4,-thiadiazole, 1,3,4-thiadiazole, oxazole, thiazole, benzopyrazole, benzimidazole, benzoxazole, benzothizole, indole, pyrrole, furan, thiophene, benzofuran, benzothiophene, pyridine, pyrimidine, pyridazine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, quinoline, isoquinoline, quinazoline, phthalazine, benzopyridazine, benzopyrazine, carbazole, dibenzofuran, dibenzothiophene, benzoxazine, phthalimide, benzopyran, dibenzopyridine, pyridopyridine, pyrazolopyrimidine, tetrahydropyrimidinedione, piperidine, morpholine, tetrahydrofuran, tetrahydrothiophene, pyrrolidine, thiomorpholine, piperidine-2-one, piperidine-2,6-dione, 2,5-pyrrolidinedione, 3-morpholinone, 2-oxohexamethyleneimine, 2-oxotetramethyleneimine, 1-pyrazoline, 2-pyrazoline, pyrazolidine, 2-imidazolidinone, 2-imidazolidinethione, 2,4-imidazolidinedione, 1,2-oxathiolane, 1,3-oxathiolane, 1,3-oxathiane, 1,4-oxathiane, 2(1H)-pyrazinone, 2H-pyran-2-one, 4H-pyran-4-one, 2H-pyran-2-thione, 4H-pyran-4-thione, tetrahydropyran, tetrahydrothiopyran, 7-oxabicyclo[2.2.1]heptane,
7-azabicyclo[2.2.1]heptane, oxetane, coumarin, 1,3-dioxane, 1,4-dioxane or 1,3-dioxolane;
X29 represents -CH(alkyl)O-, -C(alkyl)2O-, -OCH2-, -CH2O-, -CH2-, a covalent bond, -C(halogen)2, -OCH2O-,
-OCH2CH2O-, -C≡C-, -OCH(alkyl)-, -OC(alkyl)2, -OCH(alkyl)O-, -OC(alkyl)2O-, -OCH(alkyl)CH2O-, -OCH(alkyl)CH(alkyl)O-, -CH(alkyl)CH(alkyl)-, -CH(alkyl)-, -C(alkyl)2-, -CH2CH2O-, -OCH2CH2-, -CH(alkyl)CH2O-, -CH2CH2-, -CH(CN)O-, -C(alkyl)(CN)O-, -CH(polyhaloalkyl)O-, -C(CN)=NO-, -C(NH alkyl)=NO-, -C[N(alkyl)2]=NO-, -C(S-alkyl)=NO-, -C(O-alkyl)=NO-, -SC(=O)O-, -NHC(=O)O-, -N(alkyl)C(=O)O-, SO, SO2, -CH2S(O)h-, -CH(alkyl)S(O)h-, -S(O)hCH2-, -SC(=S)S-, -C(=O)S-, -C(=S)-S-, -NH(alkyl)C(=O)S-,
-O(C=O)S-, -NH-, -N(alkyl)-, -N( R34)-,-SO2NH-,
-SO2N(alkyl)-, -CONH-, -CON(alkyl)-,
-SC(=O)N(alkyl)-, -S-C(=O)NH-, -NHSO2NH-,
-N(alkyl)SO2N(alkyl)-, -N(alkyl)SO2NH-,
-NHSO2N(alkyl)-, -C(O-alkyl)=N-, -C(S-alkyl)=N-,
-CH(halogen)-, -C(alkyl) (halogen)-, -CH(CN)-,
-C(alkyl)(CN)-, -NH(alkyl)NH-, -NH-N(alkyl)-;
-NH-NH-, -N=N-, -C(=O)-, -C(=O)C(=O)-,
-CH(O-alkyl)-, -CH2C(=O)-, -C(=O)CH2,
-CH(alkyl)C(=O)-, -C(=O)CH(alkyl)-, -CH=CH-,
-C(alkyl)=CH-, -CH=C(alkyl)-, -C(alkyl)=C(alkyl)-,
-C(=O)CH=CH-, -P(Y43)(Y44-alkyl)-, unsubstituted or substituted -P(Y43)(Y44-aryl) or arylene,
-Si(halogen)2-, -Si(alkyl)2, -OC(=O)N(alkyl)-,
-OCH2C(=O)N(alkyl)-, -N(alkyl)CON(alkyl)-;
-OC(=O)NH-, -NHCONH-, -SO2NHC(=O)NH-, -NHC(=S)NH-,
Figure imgf000263_0001
wherein h is a value of from 0 to 2 inclusive, R34 represents acyl, alkylsulfonyl, polyhaloalkyl, polyhaloacyl, polyhaloalkylsulfonyl or unsubstituted or substituted aroyl or arylsulfonyl and Y43 and
Y44 are independently O or S; Z5 and Z6 are independently O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl , aryl, aralkyl , alkenyl or alkynyl ; and
Y71 and Y72 are the same or different and represent hydrogen, halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, amino, alkylamino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, alkoxycarbonyl, alkylaminocarbonyl, aminocarbonyl, dialkylaminocarbonyl, dialkylaminosulfonyl, alkylaminosulfonyl, .aminosulfonyl, dialkoxyalkyl, arylsulfonyl, phosphono or phosphino;
Figure imgf000264_0001
R71 represents unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkadienyl, cycloalkatrienyl, bicycloalkyl, bicycloalkenyl, bicycloalkadienyl, tricycloalkyl, tricycloalkenyl or tricycloalkadienyl:
X30 represents -CH(alkyl)O-, -C(alkyl)2O-, -OCH2-, -CH2O-, -CH2-, a covalent bond, -C(halogen)2, -OCH2O-, -OCH2CH2O-, -C≡C-, -OCH(alkyl)-, -OC(alkyl)2, -OCH(alkyl)O-, -OC(alkyl)2O-, -OCH(alkyl)CH2O-, -OCH(alkyl)CH(alkyl)O-, -CH(alkyl)CH(alkyl)-, -CH(alkyl)-, -C(alkyl)2-, -CH2CH2O-, -OCH2CH2-, -CH(alkyl)CH2O-, -CH2CH2-, -CH(CN)O-, -C(alkyl)(CN)O-, -CH(polyhaloalkyl)O-, -C(CN)=NO-, -C(NH alkyl)=NO-, -C[N(alkyl)2]=NO-,
-C(S-alkyl)=NO-, -C(O-alkyl)=NO-, -SC(=O)O-,
-NHC(=O)O-, -N(alkyl)C(=O)O-, SO, SO2,
-CH2S(O)h-, -CH(alkyl)S(O)h-, -S(O)hCH2-,
-OC(=S)S-, -C(=O)S-, -C(=S)-S-, -NH(alkyl)C(=O)S-,
-O(C=O)S-, -NH-, -N(alkyl)-, -N(R34)-,-SO2NH-,
-SO2N(alkyl)-, -CONH-, -CON(alkyl)-,
-SC(=O)N(alkyl)-, -S-C(=O)NH-, -NHSO2NH-,
-N(alkyl)SO2N(alkyl)-, -N(alkyl)SO2NH-,
-NHSO2N(alkyl)-, -C(O-alkyl)=N-, -C(S-alkyl)=N-,
-CH(halogen)-, -C(alkyl) (halogen)-, -CH(CN)-,
-C(alkyl)(CN)-, -NH(alkyl)NH-, -NH-N(alkyl)-;
-NH-NH-, -N=N-, -C(=O)-, -C(=O)C(=O)-,
-CH(O-alkyl)-, -CH2C(=O)-, -C(=O)CH2,
-CH(alkyl)C(=O)-, -C(=O)CH(alkyl)-, -CH=CH-,
-C(alkyl)=CH-, -CH=C(alkyl)-, -C(alkyl)=C(alkyl)-,
-C(=O)CH=CH-, -P( Y43)( Y44-alkyl)-, unsubstituted or substituted -P( Y43) ( Y44-aryl) or arylene,
-Si(halogen)2-, -Si(alkyl)2, -OC(=O)N(alkyl)-, -OCH2C(=O)N(alkyl)-, -N(alkyl)CON(alkyl)-; -OC(=O)NH-, -NHCONH-, -SO2NHC(=O)NH-, -NHC(=S)NH
Figure imgf000265_0001
wherein h is a value of from 0 to 2 inclusive, R34 represents acyl, alkylsulfonyl, polyhaloalkyl, polyhaloacyl, polyhaloalkylsulfonyl or unsubstituted or substituted aroyl or arylsulfonyl and Y43 and
Y44 are independently O or S; Z7 and Z8 are independently O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y73 and Y74 are the same or different and represent hydrogen,halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, aryl, polyhaloalkylsulfonyl, alkylamino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy and polyhaloalkylsulfonyloxy;
Figure imgf000266_0001
wherein:
B21 represents -CH2C(CH3)2SCH2-,
-CH2CH=C(CH2)OCH2-,
-CH2CH2SCH2CH(CH3)-,
-CH2CH2SCH2CH2-, -CH2SCH2CO-,
-COCH2C(CH3)2CH2CO-,
-COCH2CH(C6H5)CH2CO-,
-CONH(C6H5)CH2CH2O-, -COC(CH3)2NHCO-,
-CH2CH2N(C6H5)CH2CH2-,
-CH2N(C6H5)CH2CH2-,
-CH2CH2CH(C6H5)CH2CH2-,
-CO(CH2)3CO-, -CO(CH2)2CO-,
-COCH2CH(CH3)CH2CO-, -COCH(CH3)CH2CO-,
-COC(CH3)2CH2CO-,
-COC(CH3)2C(CH3)2CO-, -CO(CH2)4CO-, -CO(CH2)5CO-, -CO(CH2)5CH2-, -CO(CH2)4CH2-, -CO(CH2)3CH2-, -CO(CH2)2CH2-, -COCH2SCH2CO-,
-COCH2N(R52)CH2CO-, -COCH2OCH2CO-,
-COCH2SCS-, -COCH=CH-N=CH-,
-CH2CH(C6H2)CH2-N=CH- or -CO2-CH2CH2- wherein R52 represents hydrogen, alkenyl; unsubstituted or substituted aryl or alkaryl; Z9 and Z10 are independently O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y75 and Y76 are the same or different and represent hydrogen,halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, amino, alkylamino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino;
Figure imgf000267_0001
R72represents unsubstituted or substituted phenyl or 1- or 2-naphthyl;
X31 represents -OCH2-, -CH2-, a covalent bond, -C(halogen)2, -C≡C-, -OCH(alkyl)-,
-OC(alkyl)2, -CH(alkyl)CH(alkyl)-, -CH(alkyl)-,
-C(alkyl)2-, -OCH2CH2-, -CH2CH2-, SO, -S-,
SO2, -CH2S(O)h-, -CH(alkyl)S(O)h-,
-S(O)hCH2-, -CH(halogen)-, -C(alkyl) (halogen), -CH(CN)-, -C(alkyl)(CN)-, or -C(=O)-, -CH(O-alkyl)-, -CH2C(-O)-, -C(=O)CH2, -CH(alkyl)C(=O)-, -C(=O)CH(alkyl)-, -CH=CH-, -C(alkyl)=CH-, -CH=C(alkyl)-, -C(alkyl)=C(alkyl)-, -C(=O)CH=CH-, arylene, -Si(halogen)2-, -Si(alkyl)2,
Figure imgf000268_0002
wherein h is a value of from 0 to 2 inclusive;
Z11 represents O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y77, Y78 and Y79 are the same or different and represent hydrogen,halogen, alkyl, hydroxy, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, aIkylamino, amino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino, with the proviso that when Y77 is halogen and
Y79 is hydrogen then Y78 cannot be amino, alkylamino, dialkylamino or acylamino and with the further proviso that when Y77 and Y78 are the same halogen then Y79 cannot be hydrogen or hydroxy;
Figure imgf000268_0001
R73 represents an unsubstituted or substituted, unsaturated or saturated, aromatic or non-aromatic heterocyclic ring system selected from isoxazole, isothiazole, pyrazole, imidazole, 1,2,4-triazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4,-thiadiazole, 1,3,4-thiadiazole, oxazole, thiazole, benzopyrazole, benzimidazole, benzoxazole, benzothizole, indole, pyrrole, furan, thiophene, benzofuran, benzothiophene, pyridine, pyrimidine, pyridazine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, quinoline, isoquinoline, quinazoϊine, phthalazine, benzopyridazine, benzopyrazine, carbazole, dibenzofuran, dibenzothiophene, benzoxazine, phthalimide, benzopyran, dibenzopyridine, pyridopyridine, pyrazolopyrimidine, tetrahydropyrimidinedione, piperidine, morpholine, tetrahydrofuran, tetrahydrothiophene, pyrrolidine, thiomorpholine, piperidine-2-one, piperidine-2,6-dione, 2,5-pyrrolidinedione, 3-morpholinone, 2-oxohexamethyleneimine, 2-oxotetramethyleneimine, 1-pyrazoline, 2-pyrazoline, pyrazolidine, 2-imidazolidinone, 2-imidazolidinethione, 2,4-imidazolidinedione, 1,2-oxathiolane, 1,3-oxathiolane, 1,3-oxathiane, 1,4-oxathiane, 2(1H)-pyrazinone, 2H-pyran-2-one, 4H-pyran-4-one, 2H-pyran-2-thione, 4H-pyran-4-thione, tetrahydropyran, tetrahydrothiopyran, 7-oxabicyclo[2.2.1]heptane,
7-azabicyclo[2.2.1]heptane, oxetane, coumarin, 1,3-dioxane, 1,4-dioxane or 1,3-dioxolane; X32 represents -OCH2-, -CH2-, a covalent bond, -C(halogen)2, -C≡C-, -OCH(alkyl)-, -OC(alkyl)4, -CH(alkyl)CH(alkyl)-, -CH(alkyl)-,
-C(alkyl)2-, -OCH2CH2-, -CH2CH2-, SO, -S-,
SO2, -CH2S(O)h-, -CH(alkyl)S(O)h-,
-S(O)hCH2-, -CH(halogen)-, -C(alkyl) (halogen)-,
-CH(CN)-, -C(alkyl)(CN)-, -C(=O)-, -CH(O-alkyl)-,
-CH2C(=O)-, -C(=O)CH2, -CH(alkyl)C(=O)-,
-C(=O)CH(alkyl)-, -CH=CH-, -C(alkyl)=CH-,
-CH=C(alkyl)-, -C(alkyl)=C(alkyl)-, -C(=O)CH=CH-, arylene, -Si(halogen)2-, -Si(alkyl)2,
Figure imgf000270_0001
wherein h is a value of from 0 to 2 inclusive;
Z12 represents O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y80, Y81 and Y82 are the same or different and represent hydrogen,halogen, alkyl, hydroxy, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, alkylamino, amino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino;
Figure imgf000271_0001
R74 represents unsubstituted or substituted alkyl, alkenyl, alkynyl, cyploalkyl cycloalkenyl, cycloalkadienyl, cycloalkatrienyl, bicycloalkyl, bicycloalkenyl, bicycloalkadienyl, tricycloalkyl, tricycloalkenyl or tricycloalkadienyl;
X33 represents -OCH2-, -CH2-, a covalent bond, -C(halogen)2, -C≡C-, -OCH(alkyl)-, -OC(alkyl)2, -CH(alkyl)CH(alkyl)-, -CH(alkyl)-,
-C(alkyl)2-, -OCH2CH2-, -CH2CH2-, SO, -S-,
SO2, -CH2S(O)h-, -CH(alkyl)S(O)h-,
-S(O)hCH2-, -CH(halogen)-, -C(alkyl) (halogen)-,
-CH(CN)-, -C(alkyl)(CN)-, or -C(=O)-, -CH(O-alkyl)-, -CH C(=O)-, -C(=O)CH2, -CH(alkyl)C(=O)-, -C(=O)CH(alkyl)-, -CH=CH-, -C(alkyl)=CH-, -CH=C(alkyl)-, -C(alkyl)=C(alkyl)-, -C(=O)CH=CH-, arylene, -Si(halogen)2-, -Si(alkyl)2,
Figure imgf000271_0002
wherein h is a value of from 0 to 2 inclusive;
Z13 represents O, S, H2-H2 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl: and Y83, Y84 and Y85 are the same or different and represent hydrogen, halogen, alkyl, hydroxy, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, alkylamino, amino, dialkylammo, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy or polyhaloalkylsulfonyloxy; in which the permissible substituents for formulae (i) through (xxxi) above are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylammocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl , haloalkynyl , alkoxyalkyl , aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000274_0001
or
Figure imgf000274_0002
R1 - X - R36 (xxxii)
Figure imgf000274_0003
wherein:
Y62, Y63, Y64, Y65 and Y66 are the same or different and are halogen;
R1 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formaraidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, or a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxypbosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium, -X, = X, -X = R3, X-R3,
-X - R3
or
Figure imgf000277_0001
; or
Figure imgf000277_0002
R1 is a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylammocarbonyl, diaIkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl , alkenyloxy, alkynyl , alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfcnyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphmothioyl, alkylhydroxyphosphmyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 = X-R3
-X - R3
Figure imgf000279_0001
or
Figure imgf000279_0002
X is a covalent single bond or double bond, a substituted or unsubstituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylammocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylarainothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
or
Figure imgf000281_0001
; and
Figure imgf000282_0001
R36 is a substituted or unsubstituted, asymmetrical heterocyclic ring system having at least three nitrogen atoms which are selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylammocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacylrxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
—X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000284_0001
or
Figure imgf000284_0002
wherein:
R3 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl)amino, aralkylamino, alkoxyalkyIphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X- R3,
-X - R3
Figure imgf000286_0001
or
Figure imgf000287_0001
R3 is a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are; one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts , alkoxycarbonylamino , alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with, a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000289_0001
or
Figure imgf000289_0002
Y1 and Y4 are independently oxygen or sulfur;
Y2 and Y3 are independently oxygen, sulfur, amino or a covalent bond; and
R4 and R5 are independently hydrogen or substituted or unsubstituted alkyl, polyhaloalkyl, phenyl or benzyl in which the permissible substituents are the same or different and are one or moris hydrogen, halogen, alkylcarbonyl , alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formaittido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3
or
Figure imgf000291_0001
Figure imgf000291_0002
The heterocyclic nitrogen-containing compounds encompassed within formula 1, can be prepared by conventional methods known in the art, and many may be available from various suppliers. The novel heterocyclic nitrogen-containing compounds of formulae (i) through (xxxiii) above which may be used in the method of this invention can be prepared by reacting appropriate starting ingredients in accordance with conventional procedures described in the art as illustrated below.
The novel heterocyclic nitrogen-containing compounds of formula (i) can be prepared by the following general reaction scheme:
Figure imgf000292_0001
Scheme I
wherein R24, X10, a, j and Y19 are as defined hereinabove. Reactions of this general type for preparing substituted pyridines including process conditions are described for example by Mertel, H.E., The Chemistry of Heterocyclic Compounds, Pyridine and Derivatives-Part Two, Halopyridines, P. 351, Interscience, Wiley, New York (1961). Intermediates such as 2,4,6-trichloropyridine are described in U.S. Patent 3.830,820. other preparation methods for the novel compounds of formula (i) are described in Fuson. R.C., Advanced Organic Chemistry, p. 124, Wiley, New York (1950), and Ochiai, E., Aromatic Amine Oxides, p. 21, Elsevier, New York (1967).
The novel heterocyclic nitrogen-containing compounds of formula (ii) can be prepared by the following general reaction scheme:
Figure imgf000293_0001
Scheme II
wherein R25, X11, b and Y20 are as defined hereinabove. Reactions of this general type for preparing substituted pyrazines including process conditions are described for example in U.S. Patent 4.254,125.
The novel heterocyclic nitrogen-containing compounds of formula (iii) can be prepared by the following general reaction scheme:
Figure imgf000293_0002
Scheme III wherein R26, X12, Y21, Y22 and Y23 are as defined hereinabove and Y49 is halogen. Reactions of this general type for preparing 2-substituted pyrimidines including process conditions are described for example by Hurst, D.T., An
Introduction to the Chemistry and Biochemistry of
Pyrimidines, Purines and Pteridines, pp. 49-53,
Wiley, New York (1980). Intermediates in which Y21 and Y23 are alkylthio are described by
Eilingsfeld, H. and Schevermann. H. , Chem. Ber., 100. pp. 1874-1891 (1967). Other preparation methods for the novel compounds of formula (iii) such as the Rembry-Hull pyrimidine synthesis are described in Brown. D.J., The Pyrimidines; The Chemistry of Heterocyclic Compounds, pp. 98, 169-170. 166, Interscience. Wiley, New York (1960). The novel heterocyclic nitrogen-containing compounds of formula (iv) can be prepared by the following general reaction scheme:
Figure imgf000294_0001
Scheme IV wherein R27, X13, Y24, Y25, Y26 and Y49 are as defined hereinabove. Reactions of this general type for preparing 4-substituted pyrimidines including process conditions are described for example by Josima, T., et. al. Sankyo Kenkyusho
Newpo. 12., pp. 114-120 (1980).
The novel heterocyclic nitrogen-containing compounds of formula (v) can be prepared by the following general reaction scheme:
Figure imgf000295_0001
Scheme V
wherein R28, X14 , Y27, Y28 and Y29 are as defined hereinabove. Reactions of this general type for preparing 5-substituted pyrimidines including process conditions and intermediate preparations are described for example by Fieser, L.F. and Fieser, M., Organic Chemistry, p. 310, Heath, Boston (1972) also Brown, D.J., The Pyrimidines; The Chemistry of Heterocyclic Compounds, pp. 50, 166, Interscience, Wiley, New York (1962). The novel heterocyclic .nitrogen-containing compounds of formula (vi) can be prepared by the following general reaction scheme:
Figure imgf000296_0001
Scheme VI wherein R29, X15, Y30, Y31, Y32 and Y49 are as defined hereinabove. .Reactions of this general type for preparing 3-substituted pyridazines including process conditions and intermediate preparations are described for example by Jojima, T. et al., Agric. Biol. Chem., 32, (11), 1376-1381 (1968) and Eilingsfeld, H. and Schevermann, H., Chem. Ber., 100, 1874-1891 (1967).
The novel heterocyclic nitrogen-containing compounds of formula (vii) can be prepared by the following general reaction scheme:
Figure imgf000296_0002
Scheme VII wherein R30, X16, Y33, Y34, Y35 and Y49 are as defined hereinabove. Reactions of this general type for preparing 4-substituted pyridazines including process conditions and intermediate preparations are described for example by Jojime, T. et al., Agric. Biol. Chem., 32, (11), 1376-1381
(1968).
The novel heterocyclic nitrogen-containing compounds of formula (viii) can be prepared by the following general reaction scheme:
Figure imgf000297_0001
Scheme VIII
wherein Y 36, Y37, Y38, Y49, d, e. R31 and X17 are as defined hereinabove. Reactions of this general type for preparing substituted
1,3,5-triazines including process conditions and intermediate preparations are described for example in German Patent 952,478, U.S. Patent 2,824,823.
Koopman, H. et al., Rec. Trav. Chim., 78, 967-980
(1959), Drabek, J. and Skrobal, M., Chem. Zvesti, 17, (7), 482-487 (1963), Hirt, R. et al., Helv. Chim. Acta. 33, 1365 (1950), and German Patent 1,076,696. Other preparation methods for the novel compounds of formula (viii) are described in U.S. Patent 4,220,765, U.S. Patent 2,691,019 and Chakrabarti. J.K. et al., J. Chem. Soc. 861 (1974). The novel heterocyclic nitrogen-containing compounds of formula (ix) can be prepared by the following general reaction scheme:
Figure imgf000298_0001
Scheme IX
wherein R32, f, X18, Y39, Y40 and Y49 are as defined hereinabove. Reactions of this general type for preparing substituted 1,3,5-triazines including process conditions and intermediate preparations are described for example in U.S. Patent 3,316,264. Intermediates such as 2,4-dichloro-6-(diethoxyphosphinyl)-1,3,5-triazine are described in Japan Patent 74 46635. Other preparation methods for the novel compounds of formula (ix) are described in Mendoza, C.E. et al., J. Ag. Food Chem., 19, (1), 41-45 (1972).
The novel heterocyclic nitrogen-containing compounds of formula (x) can be prepared by the following general reaction scheme:
Figure imgf000299_0001
Scheme X
wherein Y41, Y42, Y49 and X19 are as defined hereinabove. Reactions of this general type for preparing bis-1,3,5-triazines including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (viii) above.
The novel heterocyclic nitrogen-containing compounds of formula (xi) can be prepared by the following general reaction scheme:
Figure imgf000300_0001
Scheme XI
wherein R33, g, X20, Y52, Y53 and Y49 are as defined hereinabove. Reactions of this general type for preparing substituted 1,3,5-triazines including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (viii) above. Other preparation methods for the novel compounds of formula (xi) are described in Allen, C.F.H. and Converse, S., Org. Syn. Coll., Vol. I, 226-227, U.S. Patent 1,911,689, Bessiere-Chretien, Y. and Serne, H., Bull. Soc. Chim. France. (6). Part 2, 2039-2046 (1973), Japan Patent 28,101, Japan Patent 28,100, Japan Patent 28,098, Japan Patent 9155, Loew, P. and Weis, CD., J. Heterocyclic Chem., 13., 829-833 (1976) and Richter. G.H., Textbook of Organic Chemistry, p. 486. Wiley. New York (1967).
The novel heterocyclic nitrogen-containing compounds of formula (xii) can be prepared by the following general reaction scheme:
Figure imgf000301_0001
Scheme XII wherein R35, X21, Y45, Y46 and Y49 are as defined hereinabove. Reactions of this general type for preparing heterocyclic substituted 1,3,5-triazines including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (viii) above. Other preparation methods for the novel compounds of formula (xii) are described in Koopman, H. and Daams, J., Rec. Trav. Chim., 77, 235-240 (1958) and United Kingdom Patent 908,352.
The novel heterocyclic nitrogen-containing compounds of formula (xiii) can be prepared by the following general reaction scheme:
Figure imgf000301_0002
Scheme XIII wherein R37, R38, B14 and Y47 are as defined hereinabove. Reactions of this general type for preparing substituted azoles including process conditions and intermediate preparations are described for example by Hautzsch, A., Chem. Ber., 24, 495 (1891), Adembri. G. and Tedeschi, P., Bull. Sci. Facul. Chim. Ind. Bologna, 23, 203 (1965) and Carr, J.B. et al., J. Med. Chem., 20, (7), 934-939 (1977).
The novel heterocyclic nitrogen-containing compounds of formula (xiv) can be prepared by the following general reaction scheme:
Figure imgf000302_0001
Scheme XIV
wherein R37, R38, B14 and Y47 are as defined hereinabove. Reactions of this general type for preparing substituted azoles including process conditions and intermediate preparations are described in Pahanayak, B.K., J. Ind. Chem. Soc., 55, (3), 264-267 (1978) and Young. T.E. and Amstutz, E.D., J. Amer. Chem. Soc., 73, 4773-4775. (1951). Other preparation methods for the novel compounds of formula (xiv) are described by Tripathi, H. et al., Agric. Biol. Chem., 37, 1375 (1973) and Young, T.E. and Amstutz, E.D., J. Amer. Chem. Soc. 73, 4773-4775 (1951).
The novel heterocyclic nitrogen-containing compounds of formula (xv) can be prepared by the following general reaction scheme:
Figure imgf000303_0001
Scheme XV
wherein R41, R42, and B15 are as defined hereinabove. Reactions of this general type for preparing substituted 1,2,4-azoles including process conditions and intermediate preparations are described by Selim, M. and Selim, M. , Bull. Soc. Chim. France. 1219-1220 (1967).
The novel heterocyclic nitrogen-containing compounds of formula (xvi) can be prepared by the following general reaction scheme:
Figure imgf000304_0001
Scheme XVI
wherein R41, R42, B15 and Y49 are defined hereinabove. Reactions of this general type for preparing substituted 1,3,4-azoles including process conditions and intermediate preparations are described by Koopman, H. et al., Rec. Trav. Chim, 78, 967-980 (1959). A useful intermediate is described in United Kingdom Patent 913,910.
The novel heterocyclic nitrogen-containing compounds of formula (xvii) can be prepared by the following general reaction scheme:
Figure imgf000304_0002
Scheme XVII wherein R45, R46, R47, R48, B16 and Y48 are as defined hereinabove. Reactions of this general type for preparing substituted benzazoles including process conditions and intermediate preparations are described by Hugershoff, A., Chem. Ber. 36, 3121-3134 (1903) and Young. T.E. and Amstutz, E.D., J. Amer. Chem. Soc., 73, 4773-4775 (1951).
The novel heterocyclic nitrogen-containing compounds of formula (xviii) can be prepared by the following general reaction scheme:
Figure imgf000305_0001
Scheme XVIII
wherein R45, R46, R47, R48, B16 and Y48 are as defined hereinabove. Reactions of this general type for preparing substituted benzisoxazoles including process conditions and intermediate preparations are described in Comprehensive Heterocyclic Chemistry, Vol. 16, p. 58, Pergamon Press. New York (1984). The novel heterocyclic nitrogen-containing compounds of formula (xix) can be prepared by the following general reaction scheme:
Figure imgf000306_0001
Scheme XIX
wherein R 50, B17, Y54, Y55 and Y49 are as defined hereinabove. Reactions of this general type for preparing substituted 1,3,5-triazines including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (viii) above. Other preparation methods for the novel compounds of formula (xix) are described by Beech, W.F., J. Chem. Soc., (C), 466-472 (1967).
The novel heterocyclic nitrogen-containing compounds of formula (xx) can be prepared by the following general reaction scheme:
Figure imgf000307_0001
Scheme XX
wherein R51, B18, B19, Y56, Y57 and Y49 are as defined hereinabove. Reactions of this general type for preparing substituted
1,3,5-triazines including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (viii) above.
The novel heterocyclic nitrogen-containing compounds of formula (xxi) can be prepared by the following general reaction scheme:
Figure imgf000307_0002
Scheme XXI wherein B20 Y58, Y59 and Y49 are as defined hereinabove. Reactions of this general type for preparing substituted 1,3,5-triazines including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (viii) above.
The novel heterocyclic nitrogen-containing compounds of formula (xxii) can be prepared by "the following general reaction scheme:
Figure imgf000308_0001
Scheme XXII
wherein R53, X25, Y60, Y61 and Y49 are as defined hereinabove. Reactions of this general type for preparing substituted 1,3,5-triazines including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (viii) above.
The novel heterocyclic nitrogen-containing compounds of formula (xxiii) can be prepared by the following general reaction scheme:
Figure imgf000309_0001
Scheme XXIII
wherein R54, X26, Y50 and Y51 are as defined hereinabove. Reactions of this general type for preparing hexahydro-1,3,5-triazines including process conditions are described for example by
Meyers. A.I. et al., J. Amer. Chem. Soc., 91, 763
(1969). The preparation of appropriate intermediates is similar to procedures employed for preparing compounds of formula (viii) above.
The novel heterocyclic nitrogen-containing compounds of formula (xxiv) can be prepared by the following general reaction scheme:
Figure imgf000309_0002
Scheme XXIV wherein R68, X27, Z1, Z2, Y67 and Y68 are as defined hereinabove. Reactions of this general type for preparing substituted maleimides including process conditions and intermediate preparations are described for example in Japan Patent 75,117,929. other preparation methods for the novel compounds of formula (xxiv) are described in U.S. Patent 3,129,225 and Japan Patent 75,132,129 The novel heterocyclic nitrogen-containing compounds of formula (xxv) can be prepared by the following general reaction scheme:
Figure imgf000310_0001
Scheme XXV wherein R69, X28, Z3, Z4, Y69 and Y70 are as defined hereinabove. Reactions of this general type for preparing substituted maleimides including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (xxiv) above.
The novel heterocyclic nitrogen-containing compounds of formula (xxvi) can be prepared by the following general reaction scheme:
Figure imgf000310_0002
Scheme XXVI wherein R , X , Z , Z Y and Y 70 29 5 6, 71 72 are as defined hereinabove. Reactions of this general type for preparing substituted maleimides including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (xxiv) above.
The novel heterocyclic nitrogen-containing compounds of formula (xxvii) can be prepared by the following general reaction scheme:
Figure imgf000311_0001
Scheme XXVII wherein R71, X30, Z7, Z8, Y73 and Y74 are as defined hereinabove. Reactions of this general type for preparing substituted maleimides including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (xxiv) above.
The novel heterocyclic nitrogen-containing compounds of formula (xxviii) can be prepared by the following general reaction scheme:
Figure imgf000311_0002
Scheme XXVIII wherein B21, Z9, Z10, Y75 and Y76 are as defined hereinabove. Reactions of this general type for preparing substituted maleimides including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (xxiv) above.
The novel heterocyclic nitrogen-containing compounds of formula (xxix) can be prepared by the following general reaction scheme:
Figure imgf000312_0001
Scheme XXIX
Figure imgf000312_0002
wherein R72, Y31, Z11, Y77, Y78 and Y79 are as defined hereinabove. Suitable halogenating agents include, for example, PCL5, POCl3, PBr5 and POBr3 and mixtures thereof. Reactions of this general type for preparing substituted pyridazinones including process conditions and intermediate preparations are described for example in Yuki Gosei Kagaku Kyotai Shi 28, (4), 462-463 (1970). Other preparation methods for the novel compounds of formula (xxix) are described in Yakugaku Zasshi 86, (12), 1168-1172 (1966), Acta Dol. Pharm. 36, (3), 301-306 (1979), U.S. Patent 2,963,477, Japan Patent 6,822,309, Org. Prep. Proced. Int 17, (2), 107-114 (1985), Arm. Khim. Zh. 21, (6), 515-520 (1968) and German Patent 1,948,550.
The novel heterocyclic nitrogen-containing compounds of formula (xxx) can be prepared by the following general reaction scheme:
Figure imgf000313_0001
Scheme XXX wherein R73, X32, Z12, Y80, Y81 and Y82 are as defined hereinabove. Reactions of this general type for preparing substituted pyridazinones including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (xxix) above.
The novel heterocyclic nitrogen-containing compounds of formula (xxxi) can be prepared by the following general reaction scheme:
Figure imgf000313_0002
wherein R74, X33, Z13, Y83, Y84 AND Y85 are as defined hereinabove. Reactions of this general type for preparing substituted pyridazinones including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (xxix) above.
The novel heterocyclic nitrogen-containing compounds of formula (xxxii) can be prepared by the following general reaction scheme:
R1 X-H + Y49 - R1-X-R36
Scheme XXXII
wherein R1, X, R36 and Y49 are as defined hereinabove. Reactions of this general type for preparing substituted asymmetrical compounds including process conditions and intermediate preparations are simi.lar to the procedures employed for preparing compounds of formula (viii) above using appropriate starting ingredients.
The novel heterocyclic nitrogen-containing compounds of formula (xxxiii) can be prepared by the following general reaction scheme:
Figure imgf000315_0001
Scheme XXXIII wherein R1, Y62, Y63, Y64, Y65, Y66 and X are as defined hereinabove. Reactions of this general type for preparing substituted cyclotriphosphazenes including process conditions and intermediate preparations are similar to the procedures employed for preparing compounds of formula (viii) above using appropriate starting ingredients.
In addition to the above, other illustrative procedures which may be employed in preparing heterocyclic nitrogen-containing compounds encompassed within formula 1 are described, for example, in the following: Italy Patent 589,543, Italy Patent 588,280, United Kingdom Patent 872,313, Canada Patent 659,610, PCT Application AU81/00046, U.S. Patent 3,203,550, U.S. Patent. 3,931,165, U.S. Patent, 2,720,480, U.S. Patent 4,038,197, U.S. Patent 3,682,903. U.S. Patent 3,775,406, U.S. Patent 3,932,167, U.S. Patent 4,390,538, U.S. Patent 3,361,746, U.S. Patent 4,414,221, U.S. Patent 4,237,127, U.S. Patent 3,951,971 and U.S. Patent
3,973,947, The antitranspirant compounds of formula 1, have been found to significantly reduce plant and crop usage of water, i.e., reduce transpiration rate, and increase the resistance of plant leaf surfaces to the loss of moisture vapor, i.e., increase diffusive resistance. In addition, the antitranspirant compounds used in this invention are substantially non-inhibiting of photosynthetic light-requiring reactions, substantially non-phytotoxic to growing plants and serve to increase crop yields in comparison with untreated crops at similar conditions, especially in regions where plants are subject to moisture stress conditions. The antitranspirant compounds used in this invention provide for the conservation of soil moisture by reducing plant and crop usage of water during certain development periods, e.g., vegetative period, thereby making the unused water available at other periods of plant or crop development, e.g., reproductive growth period.
As indicated above, stomata are minute openings in the epidermis of plant leaf surfaces through which occurs gaseous interchange between the atmosphere and the intercellular spaces within the leaf. It is believed that the antitranspirant compounds of formula 1 effectively reduce the transpiration rate in plants by closing plant stomata or constricting plant stomatal openings to such a degree that moisture loss is reduced and, in addition, the compounds exhibit substantially no detrimental effect on photosynthetic electron flow. The photosynthetic process in plants consists of light-requiring reactions, i.e., light reactions, and non-light-requiring reactions, i.e., dark reactions. The dark reactions in general involve a complex of enzyme-mediated reactions which provide for the conversion of carbon dioxide to sugar. In addition to carbon dioxide, the dark reactions require reducing power and chemical energy which are produced and provided by the light reactions. In general, two light-requiring reactions are involved in plant photosynthesis and are conventionally termed Photosystem I and Photosystem II. See. for example, Salisbury. F.B. and Ross, C.W., Plant Physiology, pp. 131-135 (1978). These photosystems are interconnected by an electron transport chain, and provide reducing power and chemical energy to the dark reactions. Inhibition of either or both of these photosystems can detrimentally affect photosynthesis, thereby causing plant injury or even plant death.
The antitranspirant compounds used in this invention have been found to cause no or substantially no inhibition of Photosystem I or Photosystem II. In contrast, the herbicide atrazine is known to substantially inhibit the light reactions of photosynthesis, particularly the electron transport chain. See, for example, Jachetta, J.J. and Radosevich, S.R., Weed Science 29: 37-43 (1981). such herbicidal inhibition leads to a buildup of carbon dioxide within the leaf which causes closure of the stomates. See, for example. Smith, D. and Buchholtz, K.P., Plant Physiology 39: 572-578 (1964). Thus, unlike the antitranspirant activity of the compounds used in this invention, the antitranspirant activity of atrazine is associated with its herbicidal properties. As used herein, substantially no inhibition of photosynthetic electron transport refers to no or little inhibition of photosynthetic electron transport.
As used herein, an effective amount of a heterocyclic nitrogen-containing compound for reducing moisture loss from plants refers to an antitranspirationally effective amount of the compound sufficient to reduce transpirational moisture loss from plants without substantially inhibiting plant photosynthetic electron transport. Likewise, an effective amount of a heterocyclic nitrogen-containing compound for increasing crop yield refers to a yield enhancing effective amount of the compound sufficient to increase crop yield without sustantially inhibiting plant photosynthetic electron transport. In both instances, the effective amount of compound can vary over a wide range depending on the particular compound employed, the particular crop to be treated, environmental and climatic conditions, and the like, provided that the amount of compound used does not cause substantial inhibition of plant photosynthetic electron transport or substantial phytotoxicity, e.g., foliar burn, chlorosis or necrosis, to the plant. In general, the compound can preferably be applied to plants and crops at a concentration of from about 0.25 to 15 pounds of compound per acre as more fully described below.
The heterocyclic nitrogen-containing compounds contemplated by formula 1 may be employed according to a variety of conventional methods known to those skilled in the art. Compositions containing the compounds as the active ingredient will usually comprise a carrier and/or diluent, either liquid or solid.
Suitable liquid diluents or carriers include water, petroleum distillates, or other liquid carriers with or without surface active agents. Liquid concentrates may be prepared by dissolving one of these compounds with a nonphytotoxic solvent such as acetone, xylene, nitrobenzene, cyclohexanone or dimethylformamide and dispersing the active ingredients in water with the aid of suitable surface active emulsifying and dispersing agents.
The choice of dispersing and emulsifying agents and the amount employed are dictated by the nature of the composition and the ability of the agent to facilitate the dispersion of the active ingredient. Generally, it is desirable to use as little of the agent as is possible, consistent with the desired dispersion of the active ingredient in the spray so that rain does not re-emulsify the active ingredient after it is applied to the plant and wash it off the plant. Nonionic, anionic. or cationic dispersing and emulsifying agents may be employed, for example, the condensation products of alkylene oxides with phenol and organic acids, alkyl aryl sulfonates, complex ether alcohols, quaternary ammonium compounds, and the like.
In the preparation of wettable powder or dust compositions, the active ingredient is dispersed in and on an appropriately divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fuller's earth, and the like. In the formulation of the wettable powders, the aforementioned dispersing agents as well as lignosulfonates can be included.
The required amount of the active ingredient contemplated herein may be applied per acre treated in from 1 to 200 gallons or more of liquid carrier and/or diluent or in from about 5 to 500 pounds of inert solid carrier and/or diluent. The concentration in the liquid concentrate will usually vary from about 5 to 95 percent by weight and in the solid formulations from about 0.5 to about 90 percent by weight. Satisfactory sprays or dusts for general use contain from about 0.1 to about 100 pounds of active ingredient per acre, preferably from about 0.25 to about 15 pounds of active ingredient per acre, and more preferably from about 0.5 to about 5 pounds of active ingredient per acre.
Formulations useful in the conduct of this invention can also contain other optional ingredients such as stabilizers or other biologically active compounds, insofar as they do not impair or reduce the activity of the active ingredient and do not harm the plant being treated. Other biologically active compounds include, for example, one or more insecticidal, herbicidal, fungicidal, nematicidal, miticidal, plant growth regulators or other known compounds. Such combinations may be used for the known or other purpose of each ingredient and may provide a synergistic effect.
The antitranspirant compounds of formula l. are preferably applied to plants and crops under substantially little or no water stress conditions, or what can be considered as average or normal growing conditions. A preferred condition for compound application is prior to substantial soil moisture loss. While not wishing to be bound to any particular theory, it is believed that application of the antitranspirant compounds does not result in a reduction of the minimum total water requirements of a treated plant or crop, but rather the application of such compounds serves to promote more efficient water utilization by treated plants and crops. It is believed that the antitranspirant effect does not reduce the total amount of water needed to grow a given plant or crop except for water savings which may be realized for some crops under irrigation, but rather such antitranspirant effect is manifested by an increase in yield of treated crops having no or limited irrigation and rainfall in comparison with untreated crops at similar conditions. Additionally, the antitranspirant compounds of formula 1 are preferably applied to plants and crops under conditions which favor large gradients in water vapor pressure between the saturated atmosphere within the leaf and the atmosphere around the leaf. Such conditions include low atmospheric humidity, high light/heat loads on the leaf, and high rates of air movement.
In particular, it is believed that the application of the antitranspirant compounds of formula 1 to plants, for example, during the vegetative growth phase reduces the amount of water utilized by the plane for on the order of about a 1 to 6 week period and therefore provides for a greater amount of reserve water available in the soil during other developmental periods such as the critical reproductive growth phase. This soil moisture conservation can minimize any water deficit within plant tissues during critical developmental periods such as the reproductive growth phase resulting in increased crop yield. The antitranspirant compounds used in this invention may likewise be applied during the plant reproductive growth phase to obtain similar results.
In general, the antitranspirant compounds of formula 1 are useful for decreasing irrigation water requirements especially in dry climate regions, for protecting plants from wilting or other damage during transplantation or shipment or during severe cold weather, and for alleviating water stress in certain types of environments as indicated above.
Such compounds are useful in agriculture, horticulture and related fields and can be applied to vegetation such as non-deciduous ornamental shrubs, evergreens, trees, and the like, to protect them against winter kill. A chief cause of winter kill is an excessive loss of moisture from leaf surfaces on sunny or windy days when the ground is frozen and the root systems cannot replace the water loss. The antitranspirant compounds can also be applied to other ornamentals such as roses and other flowers, Christmas trees, and the like, to preserve freshness and retard needle drop. The antitranspirant compounds can further be used in avoiding or minimizing the effects of summer scald and transplant shock.
In addition to the above, it is recognized that the antitranspirant compounds of formula 1 may also be used to control foliar diseases on crops such as wheat and oats. See, for example, Avant Gardener, Vol. 18, No. 1, November, 1985, in which antitranspirants are used to control fungus diseases.
As used herein, plants refer in general to any agronomic or horticultural crops, ornamentals and turfgrasses. Illustrative of plants which may be treated by the antitranspirant compounds of formula 1 according to the method of this invention include, for example, corn, cotton, sweet potatoes, white potatoes, alfalfa, wheat, rye, upland rice, barley, oats, sorghum, dry beans, soybeans, sugar beets, sunflowers, tobacco, tomatoes, canola, deciduous fruit, citrus fruit, tea, coffee, olives, pineapple, cocoa, banana, sugar cane, oil palm, herbaceous bedding plants, woody shrubs, turfgrasses, ornamental plants, evergreens, trees, flowers, and the like. As used herein, crops refer in general to any of the illustrative agronomic or horticultural crops above. Transplanted stock as used herein refers in general to tobacco, tomatoes, eggplant, cucumbers, lettuce, strawberries, herbaceous bedding plants, woody shrubs, tree seedlings and the like.
The antitranspirant compounds contemplated herein reduce transpirational moisture loss from plants and increase crop yields. Such compounds have a high margin of safety in that when used in sufficient amount to provide an antitranspirant effect or yield enhancing effect, they do not inhibit plant photosynthetic electron transport or burn or injure, the plant, and they resist weathering which includes wash-off caused by rain, decomposition by ultraviolet light, oxidation, or hydrolysis in the presence of moisture or, at least, such decomposition, oxidation, and hydrolysis as would materially decrease the desirable antitranspirant characteristic of the active ingredient or impart undesirable characteristics, for instance, phytotoxicity, to the active ingredients. Mixtures of the active compounds may be employed if desired as well as combinations of the active compounds with other biologically active compounds or ingredients as indicated above.
This invention is illustrated by the following examples. Example I
Preparation of 2,4-dichloro-6-(4-methylphenylthio)- 1,3,5-triazine
Into a solution containing 18.4 grams (0.1 mole) of cyanuric chloride in 200 milliliters of acetone was added, with cooling at a temperature of 0-5°C and magnetic stirring, a solution containing 12.4 grams (0.1 mole) of 4-methylthiophenol and 10.7 grams (0.1 mole) of 2,6-lutidine in 50 milliliters of acetone. The solution was added at such a rate to maintain the reaction temperature at 0-5°C. The resulting mixture was magnetically stirred for a period of 2 hours, allowed to warm to room temperature, and precipitated 2,6-lutidine hydrochloride was filtered off and washed with acetone. The combined filtrates were then poured onto ice and the resulting precipitated solid was collected by filtration. The solid was washed with 100 milliliters of 10% aqueous NaOH and then 100 milliliters of water. After drying, the solid was recrystallized twice from hexane to give a crude yield of 5 grams. This material was further purified by vacuum sublimation to give 1.16 grams (0.004 mole) of pure 2,4-dichloro-6-(4-methylphenylthio)-1,3,5- triazine having a melting point of 112ºC-114ºC. Elemental analysis of the product indicated the following: Analysis: C10H7Cl2N3S
Calculated: C, 44.13; H, 2.59; N, 15.44 Found: C, 44.24; H, 2.61; N, 15.34
This compound is referred to hereinafter as Compound 1.
Example II
In a manner similar to that employed in Example I, other compounds were prepared. The structures and analytical data for Compounds 2 through 36, which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table A below. Compound 18 was obtained from Maybridge Chemical Company, Limited, Trevillet, Tintagel, Cornwall, United Kingdom, and was recrystallized three times from hexane.
Figure imgf000327_0001
Figure imgf000328_0001
Figure imgf000329_0001
Example III
Preparation of 2,4-dichloro-6-(2',3'-dichlorophenoxy)-1,3,5-triazine
Into a solution containing 18.4 grams (0.1 mole) of cyanuric chloride in 150 milliliters of acetone was added, with cooling at a temperature of 0-5°C and magnetic stirring, a solution containing 16.3 grams (0.1 mole) of 2.3-dichlorophenol and 14.3 grams (0.1 mole) of quinaldine in 50 milliliters of acetone. The solution was added at such a rate to maintain the reaction temperature at 0-5°C. The resulting mixture was magnetically stirred for a period of one hour, allowed to warm to room temperature, and precipitated quinaldine hydrochloride was filtered off and washed with acetone. The combined filtrates were then poured onto ice and the resulting precipitated solid was collected by filtration. The solid was washed with 100 milliliters of 10% aqueous NaOH and then 100 milliliters of water. After drying, the solid was crystallized from hexane to give a crude yield of 14.5 grams. This material wan further purified by vacuum sublimation to give 1.7 grams (0.005 mole) of 2,4-dichloro-6-(2',3'-dichloro-phenoxy)-1,3,5-triazine having a meltin point of 154.5ºC-156°C. Elemental analysis of the product indicated the following: Analysis: C9H3Cl4N3O Calculated: C, 34.76; H, 0.97; N, 13.51 Found: C, 34.30; H, 0.89; N, 13.80.
This compound is referred to hereinafter as Compound 37.
Example IV
In a manner similar to that employed in Example III, other compounds were prepared. The structures and analytical data for Compounds 38 through 45, which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table B below.
Figure imgf000332_0001
Example V Preparation of 2-chloro-4,6-bis(2',4'-dichlorophenoxy)-1,3,5-triazine
Into a solution containing 9.2 grams (0.05 mole) of cyanuric chloride in 100 milliliters of acetone was added, with cooling at a temperature of 0-5°C and magnetic stirring, 8.15 grams (0.05 mole) of 2,4-dichlorophenol and 7.25 grams (0.05 mole) of potassium carbonate. The ingredients were added at such a rate to maintain the reaction temperature at 0-5°C. The mixture was poured onto ice and the resulting solid precipitate was collected by filtration, washed with 100 milliliters of 10% aqueous sodium hydroxide and then with water. After drying, the solid was recrystallized from hexane. The first crop of crystals was recrystallized twice from hexane to give 2.0 grams (0.005 mole) of 2-chloro-4,6-bis(2',4'-dichlorophenoxy)-1,3,5-triazine having a melting point of 165ºC-168ºC. Elemental analysis of the product indicated the following:
Analysis: C15H6Cl5N3O2
Calculated: C, 41.18; H, 1.38; N. 9.60
Found: C, 41.41; H. 0.96; N. 9.86
This compound is referred to hereinafter as Compound 46. Example VI Preparation of 2,4-dichloro-6-(3',5'-dichlorophenoxy)-1,3,5-triazine
Into a stirred solution containing of 5.24 grams (0.032 mole) of 3.5-dichlorophenol in 15 milliliters of acetone, which was cooled to a temperature of 0-5°C, was added 3.45 grams (0.032 mole) of 2,6-lutidine followed by a solution of 5.93 grams (0.032 mole) of cyanuric chloride in 185 milliliters of acetone. The cyanuric chloride/acetone solution was added dropwise, while maintaining the temperature at 0-5ºC. After completing the feed, stirring was continued at a temperature of about 0°C for a period of one hour and the mixture was then warmed to ambient temperature. Lutidine hydrochloride was removed by filtration and the filtrate was treated with charcoal and filtered through Celite. The acetone solution was freed of solvent under reduced pressure and the residue dissolved in toluene. This solution was washed with 0.5 N NaOH (twice), then with water, dried over MgSO4 and evaporated in vacuo to give 9.1 grams of a crude solid product. Recrystallization from hexane and vacuum sublimation gave 1.0 gram (0.003 mole) of pure 2,4-dichloro-6-(3',5'-dichlorophenoxy)-1,3; 5-triazine having a melting point of 109ºC-111°C. Elemental analysis of the product indicated the following: Analysis: C9H3Cl4ON3 9 3 4 3 Calculated: C, 34.76; H, 0.97; N, 13.51
Found: C, 34,41; H, 0.90; N, 13.33
This compound is referred to hereinafter as Compound 47.
Example VII
Preparation of 4,6-dichloro-2-(3'-dimethylaminophenoxy)-1,3,5-triazine and 6-chloro-2,4-bis- (3'-dimethylaminophenoxy)-1,3,5-triazine
Into a suspension containing 4.2 grams (0.09 mole) of NaH (50% in oil) in 100 milliliters of dry tetrahydrofuran was added dropwise a solution containing 10.0 grams (0.07 mole) of 3-(N,N-dimethylamino)phenol in 200 milliliters of dry tetrahydrofuran at a temperature of 4°C. The mixture was warmed to room temperature, transferred into an addition funnel and added dropwise into a solution containing 13.4 grams (0.07 mole) of cyanuric chloride in 100 milliliters of dry tetrahydrofuran at 0ºC. This mixture was stirred at 0°C for a period of 3 hours, evaporated, and the residue extracted with hot CH2Cl2. The CH2Cl2 solution was evaporated and the residue purified by flash column chromatography on Florisil using 5% EtOAc in hexane to give 1.70 grams (0.004 mole), after recrystallization from EtOAc-hexane, of 6-chloro-2,4-bis- (3'-dimethylaminophenoxy)-1,3,5-triazine having a melting point of 134°C-136.5ºC and 0.65 gram (0.002 mole) of 4.6-dichloro-2-(3'-dimethylaminophenoxy)-1,3,5-triazine as an oil. Elemental analysis of these two products indicated the following:
4, 6-dichloro-2-(3'-dimethylaminophenoxy)-1,3,5-triazine
Analysis: C11H10Cl2N4O
Calculated: C, 46.34; H, 3.53; N, 19.65;
Cl, 24.87 Found: C, 48.69: H, 3.74; N, 17.17;
Cl, 20.88
This compound is referred to hereinafter as Compound 48.
6-chloro-2,4-bis-(3'-dimethylaminophenoxy)-1,3,5-triazine
Analysis: C19H20CIN5O2
Calculated: C, 59.14; H, 5.22: N, 18.15; O,
8.28; Cl, 9.19 Found: C, 58.52; E, 5.04; N, 17.85; O,
8.90; Cl, 9.46
This compound is referred to hereinafter as Compound 49. Example VIII
Preparation of 4, 6-dichloro-2-(4'-bromo-3',5'- dimethylphenoxy)-1,3,5-triazine
Into a solution containing 9.2 grams (0.05 mole) of cyanuric chloride in 80 milliliters of acetone was added 5.8 milliliters of 2,6-lutidine dissolved in 10 milliliters of acetone at a temperature of -60°C. A solution of 10.0 grams (0.05 mole) of 4-bromo-3,5-dimethylphenol in 30 milliliters of acetone was then added while maintaining the temperature at -60°C. The mixture was stirred for 1 hour at -60°C, 30 minutes at room temperature, and then filtered and the precipitate washed with acetone. The filtrate was poured onto ice and the resulting precipitate was collected by suction filtration. The crude product was washed with water and crystallized from hot hexane to give 1.49 grams (0.004 mole) of 4, 6-dichloro-2-(4'-bromo-3',5'-dimethylphenoxy)-1,3,5-triazine as pink-orange crystals having a melting point of 149ºC-151°C. Elemental analysis of the product indicated the following:
Analysis: C11H8BrCl2N3O
Calculated: C, 37.86; H, 2.31; N, 12.04
Found: C, 38.63; H, 2.47; N, 11.55
This compound is referred to hereinafter as Compound 50. Example IX
In a manner similar to that employed in Example VIII, other compounds were prepared. The structures and analytical data for Compounds 51 through 61, which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table C below. For the preparation of Compound 61, triisopropanolamine was used as the acid-acceptor in place of 2,6-lutidine.
Figure imgf000339_0001
Figure imgf000340_0001
Figure imgf000341_0001
Figure imgf000342_0001
Example X
Preparation of 4, 6-dichloro-2-(2'-phenylphenoxy)- 1,3,5-triazine
Into a magnetically stirred solution containing 10.83 grams (0.06 mole ) of cyanur ic chloride in 100 milliliters of acetone was added a solution containing of 11.24 grams (0.06 mole) of triisopropanolamine in 100 milliliters of acetone at a temperature of -70ºC. A solution of 10.0 grams (0.06 mole) of 2-phenylphenol in 100 milliliters of acetone was then added dropwise at a temperature of -70°C. This mixture was stirred at room temperature for a period of 1 hour, filtered, and the filtrate poured onto ice-water. After removal of the acetone solvent by evaporation, the resulting mixture was partitioned between water and CH2Cl2, the organic layer separated, dried using anhydrous Na2SO4 and evaporated. The residual product was purified by flash column chromatography using silica gel, and eluted with 5% ethyl acetate in hexane to give 6.0 grams (0.02 mole) of 4, 6-dichloro-2-(2'-phenylphenoxy)-1,3,5-triazine as an oil. Elemental analysis of the product indicated the following:
Analysis: C15H9Cl2N3O
Calculated: C, 56.63; H, 2.85;
N, 13.21; Cl, 22.29
Found: C, 55.65; H, 2.99;
N, 13.46; Cl, 24.18 This compound is referred to hereinafter as Compound 62.
Example XI
Preparation of 2,4-dichloro-6- (2'-chlorophenylamino)-1,3,5-triazine
In a manner similar to Example VIII, 4.63 grams (0.04 mole) of 2-chloroaniline and 6.69 grams (0.04 mole) of cyanuric chloride were reacted in the presence of 3.89 grams (0.04 mole) of 2,6-lutidine except that the cooling bath was removed at the end of the feed period and the stirred mixture allowed to warm to room temperature. After filtering off lutidine hydrochloride, the filtrate was freed of acetone solvent under reduced pressure and the resulting solid was crystallized from a mixture of hexane and benzene. The first crop of product yielded 1.1 grams (0.004 mole) of 2,4-dichloro-6-(2'-chlorophenyl-amino)-1,3,5-triazine having a melting point of 153°C-156°C. NMR analysis of the product indicated the following: NMR (CDCl3): 7.0-8.35 ppm (complex multiplet, aromatic and NH). This compound is referred to hereinafter as Compound 63. Example XII
Preparation of 2,4-dichloro-6- (4'-chlorophenylamino)-1,3,5-triazine
In a manner similar to Example XI, 6.94 grams (0.05 mole) of 4-chloroaniline, 10.04 grams (0.05 mole) of cyanuric chloride and 5.83 grams (0.05 mole) of 2,6-lutidine were reacted in acetone solution. On completing the feed, the reaction mixture was stirred for about 1 hour at a temperature of 0°C and then at room temperature for about 16 hours. Work up furnished after water-washing and drying 14.0 grams (0.05 mole) of 2,4-dichloro-6-(4'-chlorophenylamino)-1,3,5-triazine having a melting point of 181ºC-184°C. NMR analysis of the product indicated the following: 13C NMR (d6 acetone) 171.38. 165.29. 136.74. 130.56. 129.72. 123.79 ppm.
This compound is referred to hereinafter as Compound 64.
Example XIII
Preparation of 2,4-dichloro-6- (5',6',7',8'-tetrahvdronaphthyl-1'-amino)- 1,3,5-triazine
Into a stirred solution containing cyanuric chloride (5.0 grams. 0.03 mole) in acetone (120 milliliters) at a temperature of 0°C was added dropwise a solution containing 2,6-lutidine (3.15 milliliters, 0.03 mole) and 1-amino-5,6,7,8-tetrahydronaphthalene (3.97 grams, 0.03 mole) in acetone (200 milliliters). After 2 hours at 0°C, the reaction mixture was warmed to room temperature and stirred for a period of 1 hour. The reaction mixture was filtered, and the filtrate was filtered through silica gel and washed with acetone to afford 2,4-dichloro-6-(5',6',7',8'-tetrahydronaphthyl-1'-amino)-1,3,5-triazine as a solid (7.0 grams, 0.02 mole) haying a melting point of 158ºC-162°C. Elemental analysis of the product indicated the following:
Analysis: C13H12Cl2N4
Calculated: C, 52,89; H, 4.10; N, 18.98. Found: C, 53.03; H, 4.06; N, 18.89
This compound is referred to hereinafter as Compound 65.
Example XIV
Preparation of 4,6-dichloro-2- (4'-nitrophenylamino)-1,3,5-triazine
Into a solution containing 20 grams (0.11 mole) of cyanuric chloride in 300 milliliters of acetone was added a solution containing 15.0 grams (0.11 mole) of p-nitroaniline in 200 milliliters of acetone and a solution containing 12.6 milliliters (0.11 mole) of 2,6-lutidine in 100 milliliters of acetone. The resulting mixture was stirred at room temperature under a nitrogen atmosphere for about 16 hours. The mixture was then filtered, the filtrate poured onto ice-water, and the resulting precipitate collected to give 5.6 grams of a crude product. The crude product was recrystallized from acetone-toluene to give 3.72 grams (0.01 mole) of 4,6-dichloro-2-(4'-nitrophenylamino)-1,3,5-triazine as a yellow solid having a melting point of 240°C (dec.). Elemental analysis of the product indicated the following:
Analysis: C9H5N5O2Cl2
Calculated: C, 37.79; H, 1.76; N, 24.48;
O, 11.19; Cl, 24.79 Found: C, 38.04; H, 2.01; N, 24.20;
O, 11.14; Cl, 23.74
This compound is referred to hereinafter as Compound 66.
Example XV
Preparation of 4,6-dibromo-2-(4'-nitrophenylamino)- 1,3,5-triazine
Into a solution containing 600 milligrams (0.002 mole) of 4,6-dichloro-2-(4'-nitrophenylamino)-1,3,5-triazine prepared in Example XIV in 300 milliliters of CH2Cl2 was bubbled HBr gas at room temperature for a period of 4 hours. The resulting mixture was stored in a refrigerator for about 48 hours and an oil, which separated from CH2Cl2, was collected by decantation. The oil was rinsed with CH2Cl2 (3 X 20 milliliters) and then recrystallized from toluene to give 600 milligrams (0.002 mole) of 4,6-dibromo-2-(4'-nitrophenylamino)-1,3,5-triazine as a yellow solid. Elemental analysis of the product indicated the following:
Analysis: C9H5N5O2Br2
Calculated: C, 28.81; H, 1.34; N, 18.67
Found: C, 29.85: H, 2.75; N, 18.85
This compound is referred to hereinafter as Compound 67.
Example XVI
Preparation of 4,6-dibromo-2-(4'-chlorophenylamino)-1,3,5-triazine
In a manner similar to Example XV, 4,6-dichloro-2-(4'-chlorophenylamino)- 1,3,5-triazine was reacted with hydrogen bromide to give 4,6-dibromo-2-(4'-chlorophenylamino)-1,3,5-triazine having a melting point of 197.5ºC-200°C. Elemental analysis of the product indicated the followin.. Analysis: C9H5N4ClBr2
Calculated: C, 29.66; H, 1.39; N, 15.38;
Cl, 9.73; Br, 43.85 Found: C, 29.49; H, 1.48; N, 15.19;
Cl, 9.36; Br, 43.40
This compound is referred to hereinafter as Compound 68.
Example XVII
Preparation of 2-(4'-chlorophenylamino)-4,6- difluoro-1,3,5-triazine
Into a stirred solution containing 16.21 grams (0.12 mole) of cyanuric fluoride in 120 milliliters of toluene was added, with cooling at a temperature of -10°C to 0°C, a solution of 12.75 grams (0.10 mole) of 4-chloroaniline in 120 milliliters of toluene over a period of 2 hours. The mixture was then stirred at room temperature for 15 minutes and at a temperature of 50°C for 30 minutes. After filtering, the filtrate was reduced to one-half in volume by rotary vacuum evaporation of the solvent. The crystalline crude product (12.6 grams) was separated from the concentrated solution and, following liltering and drying, was recrystallized from toluene to give 6.3 grams (0.03. mole) of 2-(4'-chlorophenylamino)-4,6-difluoro -1,3,5-triazine as white crystals having a melting point of 144ºC-147ºC. NMR analysis of the product indicated the following: 13C NMR (d, acetone) δ
177.09 (m ), 168.21 (m), 130.75. 129.75. 124.12 ppm.
This compound is referred to hereinafter as Compound 69.
Example XVIII
Preparation of 4-chloro-6-iodo-2-(2',4'- dichlorophenoxy)-1,3,5-triazine
Into a suspension containing 6.0 grams (0.02 mole) of 4,6-dichloro-2-(2', 4'-dichlorophenoxy)-1,3,5-triazine in 60 milliliters of acetone was added a solution containing 5.8 grams (0.04 mole) of Nal in 60 milliliters of acetone. The resulting mixture was stirred and heated to a temperature of 90°C in a sealed bottle for a period of 6 hours. The mixture was then filtered, the filtrate evaporated to give 9.2 grams of solid, and 40 milliliters of methylene chloride was added to this solid and the suspension then filtered. The filtrate was evaporated and the residue was sublimed in vacuo at 90°C for 10 hours. The temperature was then raised to 160°C-190ºC and 2.0 grams of off-white solid was collected from the cold finger. This solid was recrystallized from CH3CN - water to give 1.0 gram (0.002 mole) of 4-chloro-6-iodo-2-(2',4',dichlorophenoxy)-1,3,5-triazine as a white solid having a melting point of 155ºC-158ºC. Elemental analysis of the product indicated the following: Analysis: C9H3Cl3IN3O
Calculated: C, 26.84; H, 0.75; N, 10.44;
I, 31.54. Found: C, 26.87; H, 0.77; N, 10.27;
I, 30.61
This compound is referred to hereinafter as Compound 70.
Example XIX
Preparation of 4 , 6-dibromo-2-(2',4'- dichlorophenoxy)-1,3,5-triazine
A 4.0 gram (0.01 mole) portion of 2,4-dichloro-6-(2',4'-dichlorophenoxy)-1,3,5-triazine prepared in a manner similar to Example III was dissolved in 200 milliliters of toluene. HBr gas was continuously bubbled through the refluxing mixture for a period of 5 hours. The reaction mixture was cooled to room temperature and nitrogen gas was bubbled through the mixture to remove any excess HBr. The reaction mixture was then evaporated to dryness and the residue recrystallized from CH2Cl2/hexane to give 1.97 grams (0.005 mole) of 4,6-dibromo-2-(2',4'-dichlorophenoxy)-1,3,5-triazine as silver gray crystals having a melting point of 174°C-176°C. Elemental analysis of the product indicated the following: Analysis: C9H3Br2,Cl2N3O
Calculated: C, 27.00; H, 0.75; N, 10.50;
Cl, 17.50 Found: C, 27.41; H, 0.65; N, 10.01;
Cl, 16.70
This compound is referred to hereinafter as Compound 71.
Example XX
Preparation of 2-(4'-chlorophenoxy)-4,6- difluoro-1,3,5-triazine
Into a stirred solution containing 3.91 grams (0.03 mole) of cyanuric fluoride in 150 milliliters of acetone was added dropwise a mixture containing 3.72 grams (0.03 mole) of 4-chlorophenol and 3.10 grams (0.03 mole) of 2,6-lutidine at a temperature of 0°C. After stirring for about 16 hours, the reaction mixture was poured onto ice causing an oil to separate. The oil was taken up into ether, washed with 0.5 N NaOH, then water, and dried. Evaporation gave a white solid, which was recrystallized from hexane and vacuum sublimed to give 0.47 gram (0.002 mole) of 2-(4'-chlorophenoxy)-4,6-difluoro-1,3,5-triazine having a melting point of 81ºC-82.5°C. Elemental analysis of the product indicated the followin:: Analysis: C9H9ClFN3O4
Calculated: C, 44.74; H, 1.67; N, 17.39
Found: C, 44.80; H, 1.72; N, 17.23
This compound is referred to hereinafter as Compound
72.
Example XXI
Preparation of 2-fluoro-4,6-bis-(4'- chlorophenoxy)-1,3,5-triazine
Into a mixture containing 3.72 grams (0.03 mole) of 4-chlorophenol and 3.10 grams (0.03 mole) of 2,6-lutidine in 15 milliliters of acetone was added, with magnetic stirring and cooling at a temperature of 0-5ºC. a solution containing 3.91 grams (0.03 mole) of cyanuric fluoride in 185 milliliters of acetone. After stirring at a temperature of 0-5ºC for one hour, the mixture was stirred at ambient temperature for about 70 hours. The mixture was then stirred and heated under reflux for about 28 hours , cooled to room temperature and poured onto ice to give a solid. The solid was water-washed, taken up in toluene and the resulting solution washed successively with 0.5 N NaOH and water, then dried over MgSO4 and evaporated under reduced pressure. The resulting solid was recrystallized from hexane to give 1.20 grams (0.003 mole) of a first crop of 2-fluoro-4,6-bis-(4'-chlorophenoxy)-1,3,5-triazine having a meltigng point of 149ºC-150ºC. Elemental analysis of the product indicated the following:
Analysis: C15H8N3O2Cl2F
Calculated: C, 51.15; H, 2.29; N, 11.93; F,
5.39 Found: C, 51.20; H, 2.21; N, 11.89; F,
5.16
This compound is referred to hereinafter as Compound 73.
Example XXII
Preparation of 2,4-dichloro-6-(4'-sec- butyloxyphenoxy)-1,3,5-triazine
Part A: Preparation of 4-(sec-butyloxy)phenol
Into a 500 milliliter round bottom flask under a nitrogen atmosphere was added NaOH (2.91 grams. 0.07 mole) and 125 milliliters of 1:1 water/dioxane (degassed). When all of the NaOH had dissolved, hydroquinone (4.0 grams, 0.04 mole) was added and the resulting solution immediately turned dark brown. At this time, 2-iodobutane (4.15 milliliters, 0.04 mole) dissolved in 5 milliliters of dioxane wad added and the mixture was stirred for 72 hours at room temperature and then acidified with 10% aqueous HCl solution to a pH of about 2. The aqueous solution was extracted with EtOAc (2 x 150 milliliters) and the combined extracts were washed with water, saturated NaCl, dried (MgSO4) and concentrated in vacuo to give a crude product mixture. This mixture was purified by flash chromatography to give a small amount of dialkylated product. 2.31 grams(0.01 mole) of 4-(sec-butyloxy)phenol and starting hydroquinone in order of elution. NMR analysis of the product indicated the following: NMR (CDCl3) δ 0.95 (t, 3H, J=7Hz), 1.29 (d,3H,J=6Hz), 1.29-1.40 (m,2H), 4.12 (sextet, 1H,J=6Hz), 6.35 (br s, 1H), 6.72 (s,4H) ppm.
Part B: Preparation of 2,4-dichloro-6- (4'-sec-butyloxyphenoxy)-1,3,5-triazine Into a 100 mill iliter 3-necked round bottom f lask equipped with a thermometer, addition funnel and nitrogen inlet was added cyanuric chloride (2.22 grams, 0.01 mole) dissolved in 20 milliliters of acetone. After cooling to a temperature of 0-5ºC, 4-(sec-butyloxy) phenol (2.0 grams, 0.01 mole) prepared in Part A and 2,6-lutidine (1.40 milliliters, 0.01 mole) dissolved in 20 milliliters of acetone were slowly added dropwise via the addition funnel. The temperature of the reaction was maintained between 0-5ºC during the addition. The reaction mixture was then stirred at room temperature for a period of 16 hours. After this period, the reaction mixture was filtered through a Celite pad and the pad rinsed with acetone. Ice-water was added and the oil which precipitated was extracted with EtOAc. The EtOAc layers were washed with water, dried (MgSO4) and cpncentrated to give a brown semi-solid. The crude product was purified by flash chromatography on silica (eluent 10% EtOAc/hexane) to give 2.43 grams (0.008 mole) of 2,4-dichloro-6-(4'-sec-butyloxyphenoxy)-1,3,5-triazine as pale yellow crystals having a melting point of 52.0°C-55.0°C. Elemental analysis of the product indicated the following:
Analysis: C13H13Cl2N3O2
Calculated: C, 49.70; H, 4.17; N, 13.37
Found: C, 50.26; H, 4.51; N, 13.10
This compound is referred to hereinafter as Compound 74.
Example XXIII
In a manner similar to that employed in Example XXII, other compounds were prepared. The structures and analytical data for Compounds 75 through 83, which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table D below.
Figure imgf000357_0001
Figure imgf000358_0001
Example XXIV
Preparation of 4-chloto-6-methyl-2-(2',4'- dichlorophenoxy)-1,3,5-triazine
Into a solution containing 5.0 grams (0.02 mole) of 2,4-dichloro-6-(2',4'-dichlorophenoxy)-1,3,5-triazine prepared in a manner similar to Example III in 400 milliliters of dry tetrahydrofuran was added dropwise 5.9 milliliters of a 2.7M solution of methylmagnesium bromide in ether at a temperature of 0°C. The resulting mixture was stirred at room temperature under a nitrogen atmosphere for about 18 hours. The mixture was concentrated and the residue purified by flash column chromatography on silica gel using 10% EtOAc in hexane to give 2.00 grams (0.007 mole) of 4-chloro-6-methyl-2-(2',4'-dichlorophenoxy)-1,3,5-triazine having a melting point of 107ºC-108°C. Elemental analysis of the product indicated the following:
Analysis: C10H6Cl3N3O
Calculated: C, 41.34; H, 2.08; N, 14.46;
Cl, 36.61 Found: C, 41.35; H, 2.39; N, 14.46;
Cl, 36.85
This compound is referred to hereinafter as Compound 84. Example XXV
Preparation of 4-bromo-6-methyl-2-(2',4'- dichlorophenoxy)-1,3,5-triazine
Into a solution containing 2.0 grams (0.007 mole) of 4-chloro-6-methyl-2-(2',4'-dichlorophenoxy)-1,3,5-triazine prepared in Example XXIV in 300 milliliters of CH2Cl2 was bubbled dry HBr gas for a period of 3 hours. The mixture was allowed to stand at room temperature for about 18 hours. The suspension was then filtered and the solids partitioned between NaHCO solution and CH2Cl2. The organic layer was dried over anhydrous Na2SO4 and the solvent evaporated to give 0.7 gram (0.002 mole) of 4-bromo-6-methyl-2-(2',4'-dichlorophenoxy)-1,3,5-triazine having a melting point of 123°C-127°C. Elemental analysis of the product indicated the following:
Analysis: C10H6BrCl2N3O
Calculated: C, 35.85; H, 1.81; N, 12.54;
Cl, 21.17; Br, 23.85 Foυnd: C, 36.22; H, 2.15; N, 12.46;
Cl, 22.00; Br, 21.20
This compound is referred to hereinafter as Compound 85. Example XXVI
Preparation of 4-chloro-6-methyl-2- (1-naphthoxy)-1,3,5-triazine
Into a solution containing 5.0 grams (0.02 mole) of 4,6-dichloro-2-(1-naphthoxy)-1,3,5-triazine prepared in Example IX in 300 milliliters of tetrahydrofuran at 4ºC was added dropwise 7.0 milliliters of 2.7M methylmagnesium bromide in 200 milliliters of tetrahydrofuran. The resulting mixture was stirred at room temperature for about 18 hours and then evaporated. The residue was purified by flash column chromatography on silica gel using 7% ethyl acetate in hexane to give 2.0 grams (0.007 mole) of 4-chloro-6-methyl-2-(1-naphthoxy)-1,3,5-triazine having a melting point of 80ºC-83ºC. (recrystallized from CH2Cl2-hexane). Elemental analysis of the product indicated the following:
Analysis: C14H10ClN3O
Calculated: C, 61.89; H, 3.71; N, 15.46; Cl,
13.05
Found: C, 61.86; H, 3.72; N, 15.46;
Cl, 13.07
This compound is referred to hereinafter as Compound 86. Example XXVII
Preparation of 2-chloro-4-methoxy-6- (2',4'-dichlorophenoxy) -1,3,5-triazine
Into a stirred solution containing 10.0 grams (0.03 mole) of 2,4-dichloro-6-(2',4'-dichlorophenoxy)- 1,3,5-triazine in 200 milliliters of acetone was added 3.49 grams (0.03 mole) of 2,6-lutidine at a temperature of 0°C-5°C. To this mixture was added dropwise 1.03 grams (0.03 mole) of methanol while warming to room temperature. The mixture was heated to 50ºC and maintained for about 6 hours, then cooled to room temperature and stirred for about 60 hours. Lutidine hydrochloride was filtered off, the solvent evaporated, and the residue dissolved in ether and dried over MgSO 4.
The solution was flash chromatographed on a silica column, eluting with CH2Cl2/hexane (9:1).
Evaporation of solvent gave 3.14 grams of crystalline product which was recrystallized from hexane to give 1.86 grams (0.006 mole) of 2-chloro-4-methoxy-6-(2',4'-dichlorophenoxy)-1,3,5-triazine having a melting point of 87°C-89°C. Elemental analysis of the product indicated the following:
Analysis: C10H6Cl3N3O2
Calculated: C, 38.67; H, 1.97; N, 13.71
Found: C, 38.94; H, 2.00; N, 14.09 This compound is referred to hereinafter as Compound 87.
Example XXVIII
Preparation of 4, 6-bis- (2',2',2'-trifluoroethoxy) -2-phenyl-1,3,5-triazine
Into a stirred suspension containing 1.06 grams (0.02 mole) of NaH (50% in oil) in 30 milliliters of dry tetrahydrofuran was added dropwise a solution containing 1.72 milliliters (0.01 mole) of 2,2,2-trifluoroethanol in 10 milliliters of dry tetrahydrofuran at a temperature of 4°C. This mixture was stirred at room temperature under a nitrogen atmosphere for 20 minutes. The mixture was then transferred into an addition funnel under a nitrogen atmosphere and added dropwise to a solution of 5.0 grams (0.02 mole) of 4,6-dichloro-2-phenyl-1,3,5-triazine in 60 milliliters of dry tetrahydrofuran at room temperature, stirred for about 18 hours and then evaporated to dryness. The residue was purified by flash column chromatography on silica gel using 2% EtOAc in hexane to give 0.9 gram of a crude product which was recrystallized from CH2Cl2-hexane to give 0.48 gram (0.001 mole) of 4,6-bis-(2',2',2'-trifluoroethoxy)-2-phenyl-1,3,5-triazine as white plates having a melting point of 92°C-93°C. Elemental analysis of the product indicated the following: Analysis: C13H9N3O2F6
Calculated: C, 44.20; H, 2.57; N, 11.89; F, 32.27
Found: C, 44.51; H, 2.57; N, 12.03; F, 31.56
This compound is referred to hereinafter as Compound 88.
Example XXIX
Preparation of 4-chloro-6- (2',2',2'-trifluoroethoxy) -2-phenyl-1,3,5 triazine
The column chromatography fractions from Example XXVIII were examined and a group identified as containing 4-chloro-6-(2',2',2'-trifluoroethoxy)-2-phenyl-1,3,5-triazine as a second component. These were combined and purified by preparative liquid chromatography (silica gel) using 10% ethyl acetate in hexane as the eluent to give 320 milligrams (0.001 mole) of 4-chloro-6-(2',2',2'-trifluoroethoxy)-2-phenyl-1,3,5-triazine as an oil. Elemental analysis of the product indicated the following:
Analysis: C11H7Cl1F3N3O
Calculated: C, 45.61; H, 2.44; N, 14:51; Cl, 12.24; F, 19.68
Found: C, 45.43; H, 2.41; N, 14.45;
Cl, 12.28; F, 18.02 This compound is referred to hereinafter as Compound
89.
Example XXX
Preparation of 2-chloro-4-(2',4'-dichlorophenoxy) -6-(diethoxyphosphinyl)-1,3,5-triazine
Part A. Preparation of 2,4-dichloro-6- (diethoxyphosphinyl)-1,3,5-triazine Into a stirred solution containing 36.9 grams (0.02 mole) of cyanuric chloride in 150 milliliters of toluene was added 33.2 grams (0.02 mole) of triethyl phosphite in small portions. The exothermic reaction was controlled by cooling in an ice bath until it ceased. The reaction mixture was stirred and heated for about 18 hours at a temperature of 60°C-90°C. Toluene was removed under reduced pressure and the residue extracted with hexane. After filtering through Celite.the crude product of 2,4-dichloro-6-(diethoxyphosphinyl)-1,3,5-triazine showed the following NMR spectrum (ClCl3): δ 1.15-1.65 ppm (3H, t, CH3), 4.16-4.75 (2H, pentet, CH2). This product was used in Part B without purification.
Pait B. Preparation of 2-chloro-4-(2',4'- dichlorophenoxy)-6-(diethoxyphosphinyl)- 1,3, 5-triazine
A 10 gram (0.035 mole) portion of 2,4-dichloro-6-(diethoxyphosphinyl)-1,3,5-triazine prepared in Part A was dissolved in 50 milliliters of acetone and the resulting solution was added over a period of 15 minutes to a stirred mixture of 102 grams of ice and 54 milliliters of water. To this stirred suspension was added a solution containing 5.7 grams (0.035 mole) of 2,4-dichlorophenol in 18 milliliters of 8% aqueous sodium hydroxide. This mixture was stirred at 0-5°C for 1 hour and then at room temperature for an additional 1 hour. The aqueous layer was decanted away and the organic residue taken up in ether and water-washed, dried, filtered and the solvent evaporated to give 9.1 grams (0.02 mole) of 2-chloro-4-(2',4'-dichlorophenoxy)-6-(diethoxyphosphinyl)-1,3,5-triazine as an oily residue product. Elemental analysis of the product indicated the following:
Analysis: C13H13Cl3N3O4P
Calculated: C, 37.84; H, 3.18; P, 7.51;
Cl, 25.78 Found: C, 38.93; H, 3.43; P, 7.37; Cl, 25.32
This compound is referred to hereinafter as Compound 90.
Example XXXI
Preparation of 2,4-dichloro-6- (2'-carbomethoxyphenylsulfonylamino) -1,3,5-triazine
A mixture of 5.7 grams (0.03 mole) of cyanuric chloride and 7.11 grams (0.03 mole) of the sodium salt of 2-carbomethoxybenzenesulfonamide in 150 milliliters of toluene was stirred at room temperature for a period of 20 minutes. The mixture was then heated to 80°C for 3 hours, filtered hot and the filtrate diluted with hexane and cooled. A white solid precipitated and was collected by suction and dried to give 3.0 grams (0.008 mole) of 2,4-dichloro-6-(2'-carbomethoxyphenylsulfonylamino)-1. 3,5-triazine having a melting point of 212°C-215°C. Elemental analysis of the product indicated the following:
Analysis: C11H8Cl2N4O4S.
Calculated: C, 36.38; H, 2.22; N, 15.42 Found: C, 38.36; H, 1.63; N, 15.42
This compound is referred to hereinafter as Compound 91. Example XXXII
Preparation of 2-(2',4'-dichloro-alphamethylbenzyloxy)-4,6-dichloro-1,3,5-triazine
Into a solution containing 7.4 grams (0.04 mole) of cyanuric chloride in 50 milliliters of acetone under a nitrogen atmosphere and cooled to 0ºC was added dropwise a mixture of 7.6 grams (0.04 mole) of 2,4-dichloro-alpha-methylbenzyl alcohol and 4.3 grams (0.04 mole) of 2,6-lutidine and 25 milliliters of acetone. The resulting dark red reaction mixture was stirred at 0ºC for 30 minutes during which time a white precipitate formed. Stirring at room temperature was continued for 2 days. The precipitate was then separated by filtration and the filtrate concentrated under reduced pressure. The unreacted cyanuric chloride was distilled out using a Kugelrohr apparatus (.25 mmHg, 50-70°C). The dark residue was then chromatographed on silica gel employing a 9:1 hexane - EtOAc eluent. This furnished 5.0 grams of an orange-yellow oil which was distilled using a Kugelrohr apparatus and a diffusion pump (10 -4 mm
Hg; 120ºC) to yield 2.0 grams of a colorless solid.
Recrystallization from hexane gave 1.4 grams (0.004 mole) of 2-(2',4'-dichloro-alpha-methylbenzyloxy)- 4,6-dichloro-1,3,5-triazine as colorless neecles having a melting point of 97.5ºC-99.5°C. Elemental analysis of the product indicated the following: Analysis: C11H7Cl4N3O
Calculated: C, 38.97; H, 2.08; N, 12.40
Found: C, 39.02; H, 1.82; N, 12.58
This compound is referred to hereinafter as Compound 92.
Example XXXIII
In a manner similar to that employed in Example XXXII, other compounds were prepared. The structure and analytical data for Compounds 93 through 95. which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table E below.
Figure imgf000370_0001
Example XXXIV
Preparation of 2,4-dichlorobenzaldehyde O- (4,6-dichloro-1,3,5-triazin-2-yl)oxime
Part A. Preparation of 2 , 4-dichlorobenzaldehyde oxime
Into a solution containing 8.8 grams (0.13 mole) of hydroxylamine hydrochloride in 20 milliliters of water cooled to a temperature of 0°C was added 10.6 grams (0.13 mole) of sodium bicarbonate and a solution of 14.7 grams (0.08 moles) of 2,4-dichlorobenzaldehyde in 50 milliliters of ethanol. Stirring at room temperature and under nitrogen pressure was continued for 3 1/2 hours.
The reaction mixture was then diluted with 150 milliliters of water and extracted with CH2Cl2
(3 x 100 milliliters). The combined organic layers were dried over MgSO4 and concentrated under reduced pressure to yield 15.7 grams of a colorless solid. Chromatography on silica gel using dichloromethane as the eluent furnished 14.2 grams (0.07 mole) of 2, 4-dichlorobenzaldehyde oxime as a colorless solid. The NMR spectrum of this material indicated the following: NMR (CDCl3) δ 7.21 (1H, dd, J=9,2HZ). 7.40 (1H, d, J=2Hz), 7.75 (1H,d.J=9Hz), 8.09 (1H,s), 8.49 (1H,s) ppm. Part B. Preparation of 2, 4-dichlorobenzaldehyde O-(4,6-dichloro-1,3,5 triazin-2-yl)oxime
2,4-Dichlorobenzaldehyde oxime prepared in Part A was reacted with cyanuric chloride using a procedure similar to that described in Example XXXII above. The reaction mixture was filtered to remove the precipitate and the filtrate was poured onto ice causing a yellow solid to form. The solid was separated and recrystallized from acetone-water to yield 2.1 grams (0.006 mole) of 2,4-dichlorobenzaldehyde O-(4, 6-dichloro-1,3,5-triazin- 2-yl)oxime as pale yellow needles having a melting point of 124°C-124.5°C. Elemental analysis of the product indicated the following:
Analysis: C10H4Cl4N4O
Calculated: C, 35.54; H, 1.19; N, 16.58 Found: C, 35.72; H, 1.35; N, 16.74
This compound is referred to hereinafter as Compound 96.
Example XXXV
Preparation of acetophenone O-(4,6- dichloro-1,3,5-triazin-2-yl)oxime
Acetophenone oxime and cyanuric chloride were reacted according to the procedure of Example XXXIV to give acetophenone O-(4,6-dichloro-1,3,5-triazin-2-yl)oxime having a melting point of 123°C-125°C. Elemental analysis of the product indicated the following:
Analysis: C11H8Cl2N4O
Calculated: C, 46.67; H, 2.85; N, 19.79 Found: C, 47.10; H, 2.80; N, 19.77
The compound is referred to hereinafter as Compound 97.
Example XXXVI
Preparation of 2.6-dichlorobenzaldehyde O-(4,6-dichloro-1,3,5-triazin-2-yl)oxime
Into 300 milliliters of ice cold acetone was added 18.9 grams (0.1 mole) of 2,6- dichlorobenzaldoxime and 18.4 grams (0.1 mole) of cyanuric chloride. The pH value of the resulting solution was maintained at 6 by addition of 5% sodium bicarbonate solution. After stirring for 3 hours and keeping the pH at 6, crystals precipitated and were collected by suction filtration, washed three times with 100 milliliters of 20% aqueous acetone and dried in a vacuum oven for about 18 hours at 60°C to give 4.92 grams (0.02 mole) of 2,6-dichloro-benzaldehyde O-(4,6-dichloro-1,3,5-triazin-2-yl)oxime having a melting point of 134.9ºC-135.9°C. Elemental analysis of the product indicated the followin:: Analysis: C10H4Cl4N4O
Calculated: C, 35.54; H, 1.19; N, 16.58 Found: C, 35.78; H, 1.04; N, 16.40
This compound is referred to hereinafter as Compound 98.
Example XXXVII
Preparation of N-(2,4-dichlorophenyl)-N'- (4,6-dichloro-1,3,5-triazin-2-yl)hydrazine
A 4.3 gram (0.02 mole) portion of
2.4-dichlorophenylhydrazine was treated with 5.64 grams (0.03 mole) of cyanuric chloride in the presence of 3.11 grams (0.03 mole) of 2,6-lutidine in 125 milliliters of CH2Cl2 in a manner similar to that employed in Example XXXII. After stirring for about 18 hours at room temperature, the reaction mixture was concentrated under reduced pressure and the residue recrystallized from CHCl3 to give 3.4 grams (0.01 mole) of N-(2,4-dichlorophenyl) -N'-(4,6-dichloro-1,3,5-triazin-2-yl) hydrazine as colorless needles having a melting point of 185.0°C-192.0°C (dec.). Elemental analysis of the product indicated the following:
Analysis: C9H5Cl4N5
Calculated: C, 33,26; H, 1.55; N, 21.55
Found: C, 32.88; H, 1.60; N, 20.74
This compound is referred to hereinafter as Compound 99. Example XXXVIII
Preparation of N-(2,4-dichlorophenyl) -N-(4,6-dichloro-1,3,5-triazin-2-yl) methanesulf onamide
Part A. Preparation of 2,4-dichlorophenyl (methanesulfonamide)
Into a magnetically stirred solution containing 13.5 grams (0.08 mole) of 2,4-dichloroaniline, 10.1 grams (0.1 mole) of triethylamine and 80 milliliters of dry tetrahydrofuran was added dropwise a solution containing 11.5 grams (0.1 mole) of methanesulfonyl chloride in 10 milliliters of tetrahydrofuran. A white precipitate separated as the addition proceeded, stirring at room temperature was continued for about 16 hours and the mixture was then heated to reflux for 4 hours. The product was isolated by cooling, filtering to remove the precipitate and concentrating under reduced pressure to give 21.6 grams of a yellow solid. Chromatography on silica gel using a 9:1 toluene-ethyl acetate eluent furnished 1.5 grams (0.006 mole) of 2,4-dlchlorophenyl (methanesulfonamide) as a yellowish solid. NMR analysis of the product indicated the following: NMR (CDCl3) δ 8.10 (3H,s), 7.0 (1H,bs), 7.37 (1H,dd,J:2,9 Hz), 7.55 (1H,d,J:2Hz), 7.71 (1H,d,J:9Hz) ppm. Part B. Preparation of N-(2,4-dichlorophenyl)-N- (4,6-dichloro-1,3,5-triazin-2-yl) methanesulfonamide
Using a procedure similar to that employed in Example XXXVII, 1.15 grams (0.006 mole) of cyanuric chloride was treated with 1.5 grams (0.006 mole) of 2,4-dichlorophenylmethanesulfonamide and 670 milligrams (0.006 mole) of 2,6-lutidine. A colorless precipitate was separated by filtration and the filtrate was concentrated under reduced pressure to yield 2.8 grams of a yellow solid. This was flash chromatographed on silica gel employing a 3:1 hexane-ethyl acetate eluent to give 1.6 grams of a yellow solid. Recrystallization from toluene-hexane furnished 1.0 gram (0.003 mole) of N-(2,4-dichlorophenyl)-N-(4,6-dichloro-1,3,5-triazin-2-yl)methanesulfonamide as a yellow solid having a melting point of 145°C-157°C. 200 milligrams of additional yellow needles were obtained having a melting point of 154.5ºC-157°C. NMR analysis of the product indicated the following:
NMR (CDCl3): δ 3.74 (3H,S), 7.10-7.68 (3H,m) ppm. IR (CHCl3) 1540, 1590 cm-1
13C NMR (CDCl3)δ171.60, 165.42, 136.98, 134.00, 133.08, 130.97, 130.51. 128.64, 43.50 ppm.
This compound is referred to hereinafter as Compound 100. Example XXXIX
Preparation of 2-benzyloxy-4,6-dichloro -1,3,5-triazine
Into a magnetically stirred solution containing 4.22 grams (0.04 mole) of benzyl alcohol in 15 milliliters of acetone cooled to a temperature of 0-5°C was added dropwise 4.18 grams (0.04 mole) of 2,6-lutidine followed by a solution containing 7.2 grams (0.04 mole) of cyanuric chloride in 185 milliliters of acetone. After completing the feed, the reaction mixture was stirred for about 1 hour at 0°C and then warmed to room temperature. On reaching about 20°C, a precipitate of lutidine hydrochloride separated and was filtered off. The filtrate was poured onto ice causing the crude product to precipitate. This crude product was water-washed and dried to give 5.79 grams of material. Two recrystallizations from hexane gave 0.41 gram (0.002 mole) of 2-benzyloxy-4,6-dichloro-1,3,5-triazine having a melting point of 78°C-81.5°C. NMR analysis of the product indicated the following: NMR (CDCl3) :δ 5.55 ppm (2H, s, CH2), 7.46 (5H, s, aromatic).
This compound is referred to hereinafter as Compound 101. Example XL
Preparation of 2-(2',4'-dichlorobenzyl) -4,6-dichloro-1,3,5-triazine
A 1.2 gram (0.05 mole) portion of magnesium turnings and 20 milliliters of ether were placed in a 100 milliliter 3-necked round-bottom flask under a nitrogen atmosphere. Two drops of a solution containing 9.7 grams (0.05 moles) of 2,4-dichlorobenzyl chloride in 15 milliliters of ether were added to initiate the reaction. The remaining portion of this solution was then added rapidly as to cause vigorous refluxing.
The Grignard reagent prepared above was added dropwise to a mixture of 9.2 grams (0.05 moles) of cyanuric chloride and 125 milliliters of ether cooled to a temperature of 3°C. An exotherm to 7°C and the formation of a white precipitate were observed as the addition proceeded. Stirring was continued at room temperature for about 16 hours and the resulting heterogenous mixture was filtered to remove the magnesium salt. The filtrate was washed with water and the organic phase dried over MgSO4 and concentrated under reduced pressure to give 12.6 grams of a yellow solid. A 4.0 gram portion of this material was chromatographed on silica gel using a 9:1 hexane: EtOAc eluent furnishing 2.9 grams of product. Recrystallization from hexane provided 1.7 grams (0.005 mole) of 2-(2',4'-dichlorobenzyl) -4,6-dichloro-1,3,5-triazine as colorless needles having a melting point of 110°C-112.5°C. Elemental analysis of this product indicated the following: Analysis: C10H5Cl4N3
Calculated: C, 38.87; H, 1,63; N, 13.60
Found: C, 38.71; H, 1.70; N, 13.51
This compound is referred to hereinafter as Compound 102.
Example XLI
Preparation of 2-(2',4'-dichlorophenyl) -4,6-dichloro-1,3,5-triazine
A Grignard reagent was prepared from 11.1 grams (0.04 mole) of 2,4-dichloroiodobenzene in the same manner as described in Example XL. The reagent was added dropwise to a solution of 7.5 grams (0.04 mole) of cyanuric chloride in 75 milliliters of dry tetrahydrofuran cooled to a temperature of 3°C.
This caused an exotherm to 8°C and the formation of a white solid. The reaction mixture was stirred at room temperature for 7 hours and then heated to reflux for 3 days. The solid was separated by filtration and a black filtrate was concentrated under reduced pressure. The residue was partitioned between EtOAc and water and the organic phase dried over MgSO4 and concentrated to yield 14.9 grams of a black solid. Most of the unreacted cyanuric chloride was distilled out using a Kugelrohr apparatus. The residue was then chromatographed on silica gel using a 9:1 hexane: EtOAc eluent. This furnished 5.4 grams of a crude material. Sublimation (.05 mm Hg, 80°C-85ºC) provided 2.0 grams (0.007 mole) of 2-(2',4'-dichlorophenyl)-4,6-dichloro-1,3,5-triazine as a colorless solid having a melting point of 111°C-115ºC. Elemental analysis of the product indicated the following:
Analysis: C9H3Cl4N3
Calculated: C, 36.65; H, 1.03; N, 14.25
Found: C, 34.22. H, 0.92; N, 13.20
This compound is referred to hereinafter as Compound 103.
Example XLII Preparation of 2,4-dichloro- 6-phenyl-1,3,5-triazine
A 1.40 gram portion (0.06 mole) of clean magnesium turnings was suspended in 4 milliliters of ethyl ether under a dry nitrogen atmosphere in a 50 milliliter reaction flask equipped with an additional funnel. Bromobenzene (9.48 grams. 0.06 mole) and approximately 21 milliliters of ether were charged to the flask's addition funnel and about 2 milliliters of this solution was added into the flask which was warmed to initiate the reaction. The remaining bromobenzene solution was added over about a one hour period giving a controlled rate of reflux. The mixture was stirred at room temperature for about 16 hours and then heated under ref lux. The Grignard reagent prepared above was then transferred by syringe to a dry addition funnel attached to a stirred, nitrogen-purged dry flask containing a solution of 8.15 grams (0.04 mole) of cyanuric chloride in 75 milliliters benzene which was cooled to a temperature of 3ºC. The Grignard reagent solution was fed dropwise with stirring and the resulting mixture allowed to warm to room temperature for a 4-day period. The reaction mixture was quenched with 50 milliliters of water and extracted with ether after which the organic layers were dried and evaporated free of solvent to give a solid. Crystallization from hexane gave a 4.91 gram (0.02 mole) first crop of product which was recrystallized from cyclohexane and then vacuum sublimed to give 2,4-dichloro-6-phenyl-1,3,5-triazine as a white crystalline material having a melting point of 117°C-118°C. Elemental analysis of the product indicated the following:
Analysis: C9H5Cl2N3
Calculated: C, 47.80; H, 2.23; N, 18.58
Found: C, 47.50; H, 2.26; N, 18.49
This compound is referred to hereinafter as Compound 104. Example XLIII
Preparation of 2-(1-naphthyl)- 4,6-dichloro-1,3,5-triazine
Into 0.66 gram (0.03 mole) of magnesium turnings was added a solution containing 3.77 milliliters (0.03 mole) of 1-bromonaphthalene in 50 milliliters of dry tetrahydrofuran. The resulting mixture was stirred at room temperature for 20 minutes, 150 milliliters of dry tetrahydrofuran was added and the mixture then stirred at room temperature under a nitrogen atmosphere for a period of 1 hour.
The Grignard reagent prepared above was transferred to an addition funnel and added dropwise to a solution containing 5.0 grams (0.03 mole) of cyanuric chloride in 300 milliliters of dry tetrahydrofuran at room temperature. After this mixture was stirred for a period of 3 hours, the solvent was evaporated to give a solid residue which was partitioned between 10% aqueous NaOH solution and Et2O. The Et2O layer was stirred over anhydrous Na2SO4 and evaporated and the residue purified by preparative plate chromatography (silica gel) using 20% EtOAc in hexane to give 160 milligrams (0.0006 mole) of 2-(1-naphthyl) -4,6-dichloro-1,3,5-triazine as a yellow solid having a melting point of 166ºC-167°C. Elemental analysis of the product indicated the followin:: Analysis: C13H7Cl2N3
Calculated: C, 56.54; H, 2.56;
Found: C, 55.27; H, 2.62
This compound is referred to hereinafter as Compound 105.
Example XLIV
Preparation of 2-(2-naphthyl)- 4,6-dichloro-1,3,5-triazine
In a manner similar to that employed in Example XLIII except that ethyl ether was used as the solvent in place of tetrahydrofuran and the Grignard reagent was prepared from 2-bromonaphthalene in refluxing ether over a 1.5 hour period, 2-(2-naphthyl)-4,6-dichloro-1,3,5-triazine was prepared having a melting point of 193°C-194°C. Elemental analysis of the product indicated the following:
Analysis: C13H7Cl2N3
Calculated: C, 56.54; H, 2.56; N, 15.22; Cl, 25.68 Found: C, 54.48; H, 2.63; N, 14.54; Cl, 27.98
This compound is referred to hereinafter as Compound 106. Example XLV
Preparation of 2-benzyl-4,6- dichloro-1,3,5-triazine
A Grignard reagent prepared from 1.40 grams (0.06 mole) of magnesium and 0.91 gram (0.09 mole) of benzyl chloride was reacted with 8.15 grams (0.04 mole) of cyanuric chloride in a manner similar to that employed in Example XLII. The crude product (2.70 grams) was vacuum sublimed and then resublimed to give 0.99 gram (0.004 mole) of pure 2-benzyl-4,6-dichloro-1,3,5-triazine having a melting point of 82°C-85°C. Elemental analysis of the product indicated the following:
Analysis: C10H7CI2N3
Calculated: C, 50.02; H, 2.94; N, 17.49 Found: C, 49.90; H, 2.85; N, 17.57
The compound is referred to hereinafter as Compound 107.
Example XLVI Preparation of 2-(2',4'-dichlorobenzylthio)- 4,6-dichloro-1,3,5-triazine
Part A. Preparation of 2,4-dichlorobenzyl mercaptan
A mixture of 4.8 grams (0.06 mole) of thiourea. 12.2 grams (0.06 mole) of 2,4-diehlorobenzyl chloride and 50 milliliters of ethanol was stirred and heated to reflux under a nitrogen atmosphere for 4 1/2 hours. The reaction mixture was then cooled and a solution of 6.25 grams (0.16 mole) of NaOH in 50 milliliters of water was added dropwise. After the addition was completed, the mixture was heated to reflux for 2 hours during which time it became yellow in color. Stirring at room temperature was continued for 2 days. The ethanol was then removed under reduced pressure and the aqueous residue was extracted with CH2Cl2 (6 x 100 milliliters). The combined organic layers were dried over MgSO4 and concentrated to yield
12.1 grams (0.06 mole) of 2,4-dichlorobenzyl mercaptan as a tan colored liquid. NMR analysis of the product indicated the following: NMR (CDCl3):δ1.90 (1H, t, J=8HZ), 3.79 (2H, d, J=8HZ), 7.18-7.33 (2H, m), 7.33-7.48 (1H, m) ppm.
Part B. Preparation of 2-(2',4'-dichlorobenzylthio)- 4,6-dichloro-1,3,5-triazine
Into a solution containing 6.5 grams (0.03 mole) of cyanuric chloride in acetone was added 6.7 grams (0.03 mole) of 2.4-dichlorobenzyl mercaptan prepared in Part A. A procedure similar to that employed in Example XXXII was used to prepare the product. The crude product was chromatographed on silica gel using a 1:1 hexane-toluene eluent to furnish 2.0 grams of the pu;.e product. Recrystallization provided 1.9 grams (0.006 mole) of 2-(2',4'-dichlorobenzylthio)-4,6- dichloro-1,3,5-triazine having a melting point of 55.5°C-58.5ºC. Elemental analysis of the product indicated the following: Analysis: C10H5Cl4N3S
Calculated: C, 35.22. H, 1.48; N, 12.32
Found: C, 35.56; H, 1.62; N, 12.47
This compound is referred to hereinafter as Compound 108.
Example XLVII
Preparation of 6-chloro-2,4-bis- (2',4'-dichlorobenzylthio)-1,3,5-triazine
The early chromatographic fractions from Example XLVI contained 2.3 grams of a colorless solid which was recrystallized from hexane to give 2.2 grams (0.004 mole) of 2,4-bis-(2',4'-dichlorobenzylthio)-6-chloro-1,3,5-triazine having a melting point of 76.0ºC-80.0°C. Elemental analysis of the product indicated the following:
Analysis: C17H10Cl5N3S2
Calculated: C, 41.03; H, 2.03; N, 8.44 Found: C, 41.35; H, 2.25; N, 8.93
This compound is referred to hereinafter as Compound 109. Example XLVIII
Preparation of 2-(2',4'-dichlorophenethoxy)- 4,6-dichloro-1,3,5-triazine
Part A. Preparation of 2,4-dichlorophenethyl alcohol
A 124 milliliter portion of a 1 M solution of borane-tetrahydrofuran complex in tetrahydrofuran was placed in a 500 milliliter 3-necked round-bottom flask and cooled to a temperature of 0°C with an ice bath. A solution containing 12.7 grams (0.06 mole) of 2,4-dichlorophenylacetic acid in 100 milliliters of tetrahydrofuran was added dropwise at such a rate as to maintain the temperature below 5 °C . Gas evolution was observed as the addition proceeded. After the addition was completed, the colorless mixture was heated to reflux for 1 hour and then stirred at room temperature for about 16 hours. The reaction mixture was then treated with 125 milliliters of methanol. The solvent was removed under reduced pressure and the residue was dissolved in ether and washed with 5% aqueous NaOH. The organic phase was dried over MgSO4 and concentrated to yield 12.7 grams (0.066 mole) of 2,4-dichlorophenethyl alcohol as a colorless oil. NMR analysis of the product indicated the following: NMR (CDCl3): δ 1.62 (1H, s), 2.98 (2H. t, J=7Hz), 3.88 (2H, t, J=7Hz), 7.10-7.48 (3H, m) ppm. Part B. Preparation of 2-(2',4'-dichlorophenethoxy)- 4,6-dichloro-1,3,5-triazine A solution containing 6.45 grams (0.04 mole) of cyanuric chloride in acetone was treated with 6.7 grams (0.04 mole) of 2,4-dichlorophenethyl alcohol prepared in Part A using a procedure similar to that employed in Example XXXII. The crude product was chromatographed on silica gel using a 1:1 toluene-hexane eluent. The material obtained was recrystallized from hexane to yield 2.2 grams (0.006 mole) of 2-(2',4'-dichlorophenethoxy)-4,6-dichloro-1,3,5- triazine as colorless needles having a melting point of 106.5°C-108ºC. Elemental analysis of the product indicated the following:
Analysis: C11H7Cl4N3O
Calculated: C; 38.97; H, 2.08; N, 12.40 Found: C, 39.14; H, 2.35; N, 12.54
This compound is referred to hereinafter as Compound 110.
Example XLIX Preparation of N-(4,6-dichloro-1,3,5- triazin-2-yl)-2,4-dichlorobenzamide
Into a stirred mixture containing 2.2 grams (0.01 mole) of 2,4-dichlorobenzoyl chloride, 1.7 grams (0.01 mole) of 2-amino-4,6-dichlorotriazine and 80 milliliters of acetone cooled to a temperature of 0ºC was added a solution containing 400 milligrams of NaOH in 4 milliliters of water. The NaOH solution was added at such a rate as to maintain the temperature below 4°C. Stirring was continued for a period of 3 hours after the addition was complete. The reaction mixture was then poured onto ice and the resulting milky solution was extracted with dichloromethane (4 x 75 milliliters). The combined extracts were dried over MgSO4 and concentrated under reduced pressure to give 3.6 grams of a colorless solid. Flash chromatography using a 9:1 hexane-EtOAc eluent furnished 900 milligrams of a colorless solid. This material was then dissolved in CH2Cl2 and washed with saturated aqueous NaHCO3. The organic layer was dried over MgSO4 and concentrated on the rotovap. The residue was recrystallized from toluene-hexane to yield 300 milligrams (0.001 mole) of N-(4,6-dichloro-1,3,5-triazin-2-yl)-2,4-dichlorobenzamide having a melting point of 162°C-166°C. Elemental analysis of the product indicated the following:
Analysis: C10H4Cl4N4O
Calculated: C, 35.54; H, 1.19; N, 16.58 Found: C, 36.03; H, 1.54; N, 16.23
This compound is referred to hereinafter as Compound 111. Example L
Preparation of N-(4.6-dichloro-1,3,5-triazin-2-yl) -2,4-dichloroacetanilide
Part A. Preparation of 2,4-dichloroacetanilide
Into a 100 milliliter 3-necked round bottom flask was added 20 milliliters (0.21 mole) of acetic anhydride under a nitrogen atmosphere and cooled to a temperature of 3°C with an ice bath. To this was added 13.5 grams (0.08 mole) of 2,4-dichloroaniline in small portions. The mixture was allowed to stir at room temperature for 17 hours. The colorless solid which formed was removed by filtration and dried in the vacuum oven to yield 16.5 grams (0.08 mole) of 2,4-dichloroacetanilide. NMR analysis of the product indicated the following: NMR (CDCl3): δ 2.22 (3H.s), 7.18 (1H, dd), 7.34 (1H,d), 7.40-7.78 (1H,bS), 8.28 (1H,d) ppm.
Part B. Preparation of N-(4,6-dichloro-1,3,5-triazin -2-yl)-2,4-dichloroacetanilide Using a procedure similar to that employed in Example XLIX, a mixture containing 6.0 grams (0.03 mole) of 2,4-dichloroacetanilide prepared in Part A, 5.5 grams (0.03 mole) of cyanuric chloride and 120 milliliters of acetone was treated with a solution containing 1.18 grams (0.03 mole) of NaOH in 12 milliliters of water. Work-up furnished 10.5 grams of a colorless oil which was chromatographed on silica gel using a 9:1 hexane-ethyl acetate eluent. This gave 8.0 grams of a yellowish oil which solidified on standing. Recrystallization from hexane furnished 6.4 grams (0.02 mole) of colorless prisms of N-(4,6-dichloro-1,3,5-triazin-2-yl)-2,4-dichloroacetanilide having a melting point of 106°C-108.5°C. NMR analysis of the product indicated the following: NMR (CDCl3): δ 2.82 (3H.s), 7.18 (1H,d, J=9HZ), 7.45 (1H,dd,J=2,9Hz), 7.6 (1H,d,J=2Hz) ppm.
This product is referred to hereinafter as Compound 112.
Example LI
Preparation of 2,4,-dichloro-6-phenylethynyl -1,3,5-triazine
Into ethylmagnesium bromide (49 milliliters of a 2 M solution in tetrahydrofuran, 0.1 mole) was added phenylacetylene (10 grams, 0.1 mole) in tetrahydrofuran (50 milliliters). Cyanuric chloride (12 grams. 0.07 mole) in benzene (65 milliliters) was added dropwise maintaining the reaction temperature below 25°C. After six hours of stirring the solvent was evaporated and the residue extracted with ether. The solvent was evaporated and the residue triturated with ether to afford 1.5 grams (0.006 mole) of 2,4-dichloro-6-phenylethynyl -1,3,5-triazine as a yellow solid having a melting point of 125°C-131°C. Elemental analysis of the product indicated the following: Analysis: C11H5Cl2N3
Calculated: C, 52.83; H, 2.02; N, 16.80
Found: C, 53.37; H, 2.28; N, 16.25
This compound is referred to hereinafter as Compound 113.
Example LII
Preparation of 2-chloro-4-(phenylethynyl)- 6-(2',2',2'-trifluoroethoxy)-1,3,5-triazine and 2,4-bis-(2',2',2'-trifluoroethoxy)- 6-(phenylethynyl)-1,3,5-triazine
In a manner similar to that employed in Examples XXVIII and XXIX, 2, 4-dichloro-6- phenylethynyl-1,3,5-triazine was reacted with 2,2,2-trifluoroethanol to give 2-chloro-4-(phenylethynyl)-6-(2',2',2'-trifluoroethoxy)-1,3,5- triazine having a melting point of 48ºC-51°C and also 2,4-bis-(2',2',2'-trifluoroethoxy)-6-(phenylethynyl)-1,3,5-triazine having a melting point of 68°C-72°C. Elemental analysis of the two products indicated the following:
2-chloro-4-(phenylethynyl)-6- (2',2',2'-trifluoroethoxy)-1,3,5-triazine
Analysis: C13H7ClF3N3O
Calculated: C, 49.78; H, 2.25; F, 18.17; Found: C, 50.98; H, 2.42; F, 17.11 This compound is referred to hereinafter as Compound 114.
2,4-bis-(2',2',2'-trifluoroethoxy)-6-(phenylethynyl)-1,3,5-triazine
Analysis: C15H9F6N3O2
Calculated: C, 47.76; H, 2.40; N, 11.14;
F, 30.22 Found: C, 48.42; H, 2.32; N, 11.26;
F, 29.33
This compound is referred to hereinafter as Compound 115.
Example LIII
Preparation of 2-[4-(phenylazo)phenoxy]-4, 6-dichloro-1,3,5-triazine
Into a 250 milliliter 3-neck round bottom flask equipped with a thermometer, addition funnel and nitrogen inlet was added cyanuric chloride (4.67 grams, 0.03 mole) dissolved in 30 milliliters of acetone and cooled to a temperature of 0-5ºC in an ice bath. The addition funnel was charged with a solution containing 4-phenylazophenol (5.0 grams, 0.03 mole) and 2,6-lutidine (2.91 milliliters, 0.03 mole) in 30 milliliters of acetone, and this mixture was added dropwise maintaining the reaction temperature between 0°C and 5ºC. After the addition was complete, the reaction was stirred at room temperature for 16 hours, filtered through a Celite pad, and ice-water (140 milliliters) was added. The precipitate which formed was collected on a Buchner funnel. The precipitate was dissolved in EtOAc, washed with saturated NaHCO3 and water, dried
(MgSO4) and concentrated. The crude product was recrystallized twice from hexane:CHCl3 (2:1), to give 750 milligrams (0.002 mole) of 2-[4-(phenylazo) phenoxy]-4,6-dichloro-1,3,5-triazine having a melting point of 162.0°C-164.0°C. Elemental analysis of the product indicated the following:
Analysis: C15H9Cl2N5O
Calculated: C, 52.04; H, 2.62; N, 20.23 Found: C, 52.37; H, 2.82; N, 20.20
This compound is referred hereinafter as Compound 116.
Example LIV
Preparation of 2,2'-[1,3-phenylenebis(oxy)]- bis[4,6-dichloro-1,3,5-triazine]
Into a 250 milliliter 3-neck round bottom flask equipped with a nitrogen inlet, thermometer, and addition funnel was added cyanuric chloride (13.46 grams, 0.07 mole) dissolved in 100 milliliters of acetone and cooled to a temperature of 0-5°C in an ice bath. Resorcinol (4.0 grams, 0.04 mole) and 2,6-lutidine (8.50 milliliters. 0.07 mole) dissolved in 100 milliliters of acetone were placed in the addition funnel. This solution was slowly added dropwise while maintaining the reaction temperature at 0-5ºC. The reaction was then stirred at room temperature for 16 hours. At this time the precipitate was removed by filtration through a Celite pad. Addition of ice-water (140 milliliters) to the filtrate gave an oil which was extracted from the aqueous solution with EtOAc (2 x 150 milliliters). The combined organic layers were dried
(MgSO4) and concentrated in vacuo. The crude product was purified by flash chromatography on silica (eluent 5% EtOAc/hexane) to give 2.80 grams (0.007 mole) of the 2,2'-[1,3-phenylenebis(oxy)]-bis[4,6 dichloro-1,3,5-triazine] as a white solid having a melting point of 145°C-148°C. Elemental analysis of the product indicated the following:
Analysis: C12H4Cl4N6O2
Calculated: C, 35.50; H, 0.99; N, 20.70 Found: C, 35.07; H, 0.91; N, 20.40
This compound is referred to hereinafter as Compound
117.
Example LV
In a manner similar to that employed in Example LIV, other compounds were prepared. The structures and analytical data for Compounds 118 through 121, which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table F below.
Figure imgf000396_0001
Figure imgf000397_0001
Example LVI
Preparation of bis- (4,6-dichloro-1,3,5-triazin-2-yl)amine
Into a 250 milliliter 3-neck round bottom flask equipped with a thermometer and addition funnel was added cyanuric chloride (2.78 grams. 0.02 mole) in 50 milliliters of acetone cooled to a temperature of 0-5°C. 2-Amino-4,6-dichloro-1,3,5-triazine (2.48 grams, 0.02 mole) was added and the reaction temperature was brought to 0-5°C. A cold solution of NaOH (0.6 gram. 0.02 mole) in 6 milliliters of water was slowly added dropwise over 20 minutes. The reaction mixture was then stirred at room temperature for 4 hours , and then poured into 250 milliliters of ice-water with 4.5 grams of
Na2CO3 dissolved in it. The solution was filtered to remove a solid precipitate (tris[4,6-dichloro-1,3,5-triazin-2-yl]amine) and the filtrate was acidified. A white precipitate was collected on a Buchner funnel. The resulting powdery crystals (1.51 grams) were sublimed over a 2 day period to give 0.97 gram (0.003 mole) of pure bis(4,6-dichloro-1,3,5-triazin-2-yl)amine having a melting point of 204.0ºC-207.0°C. Elemental analysis of the product indicated the following:
Analysis: C6HCl4N6
Calculated: C, 23.03; H, 0.32; N, 31.33 Found: C, 22.67; H, 1.20; N, 30.67 This compound is referred to hereinafter as Compound 122.
Example LVII
Preparation of N,N-bis(4,6-dichloro-1,3,5- triazin-2-yl)-4'-fluorobenzenamine
N,N-bis(4,6-dichloro-1,3,5-triazin-2-yl)-4'-fluorobenzenamine was obtained from Maybridge Chemical Company. Limited. Trevillet, Tintagel, Cornwall. United Kingdom, and recrystallized from toluene. The melting point was determined to be 231.0°C-233.0°C. Elemental analysis of the compound indicated the following:
Analysis: C12H4CI4FN7
Calculated: C, 35.41; H, 0.99; N, 24.08
Found: C, 34.41; H, 1.06; N, 23.82
This compound is referred to hereinafter as Compound 123.
Example LVIII
Preparation of N,N-bis(4,6-dichloro-1,3,5-triazin- 2-yl)-3'-chloro-4'-fluorobenzenamine
N,N-bis(4,6-dichloro-1,3,5-triazin-2-yl)-3'-chloro-4'-fluorobenzenamine was obtained from Maybridge Chemical Company, Limited, Trevill,et, Tintagel, Cornwall, United Kingdom, and recrystallized from toluene. The melting point was determined to be 228.5°C-229.5°C. Elemental analysis of the compound indicated the following:
Analysis: C12H3Cl5FN7
Calculated: C, 32.65; H, 0.68; N, 22.21
Found: C, 32.21; H, 0.86; N, 21.65
This compound is referred to hereinafter as Compound
124.
Example LIX
Preparation of 2,2',4,4'-tetrachlorohydrazo- 1,3,5-triazine
Into a 100 milliliter 3-neck round bottom flask equipped with a mechanical stirrer, thermometer, addition funnel and nitrogen inlet was added cyanuric chloride (3.68 grams. 0.02 mole) in 20 milliliters of tetrahydrofuran which was stirred vigorously and cooled to a temperature of -15°C to -10ºC. Hydrazine hydrate (1.90 grams, 55% hydrazine content. 0.03 mole) in 4 milliliters of water was slowly added via the addition funnel, maintaining the reaction temperature between -15°C to -10°C. After the addition was complete, the reaction was stirred at 0°C for 15 minutes. Ice-water (40 milliliters) was added and the aqueous solution was then extracted with EtOAc (2 x 100 milliliters) and the extracts dried (MgSO4) and concentrated in vacuo to give 2.92 grams (0.009 mole) of 2,2',4,4'-tetrachlorohydrazo-1,3,5-triazine as a fine white solid which started to decompose over 250°C. Elemental analysis of the product indicated the following:
Analysis: C6H2Cl4N8
Calculated: C, 21.97; H, 0.61; N, 34.17
Found: C, 23.64; H, 1.34; N, 36.23
This compound is referred to hereinafter as Compound 125.
Example LX
Preparation of 2,2',4,4'-tetrachloroazo- 1,3,5-triazine
Into a 250 millliter 3-neck round bottom flask equipped with a septum, outlet to acid trap and stopper was added 2,2',4,4'-tetrachlorohydrazo-1,3,5-triazine (3.20 grams, 0.01 mole) and 100 milliliters of CHCl3. Sodium bicarbonate (1.64 grams, 0.02 mole) dissolved in 50 milliliters of water was added. The two phase solution was slowly stirred so that the phases remained separate. A slow stream of Cl2 gas was then bubbled through the CHCl3 layer until the CHCl3 layer was homogeneous and deep red, i.e., about 75 minutes. At this time the CHCl3 layer was separated and washed with water, dried (Na2SO4) and concentrated in vacuo to give orange crystals which were slurried in ether, cooled and filtered. The resulting pale orange solid was recrystallized from CHCl3 to give 2.1 grams (0.006 mole) of
2,2',4,4'-tetrachloroazo-1,3,5-triazine having a melting point of 186.0°C-190.0ºC. Elemental analysis of the product indicated the following:
Analysis: C6Cl4N8 Calculated: C, 22.11; H, 0.00; N, 34.38 Found: C, 22.78; H, 0.28; N, 33.98
This compound is referred to hereinafter as Compound 126.
Example LXI
Preparation of 2,4-dichloro-6- (4'-formyl-2'-methoxyphenoxy)-1,3,5-triazine
Into a solution containing cyanuric chloride (5.0 grams, 0.03 mole) in acetone (140 milliliters) at 0°C was added dropwise a solution containing 2,6-lutidine (3.15 milliliters, 0.03 mole) and 4-hydroxy-3-methoxybenzaldehyde (4.125 grams, 0.03 mole) in acetone (25 milliliters) while maintaining the temperature below 5°C. After 2 hours of stirring, the reaction mixture was filtered, and the filtrate filtered through silica gel and washed with acetone to afford 650 milligrams (0.002 mole) of 2,4-dichloro-6-(4'-formyl-2'-methoxyphenoxy)-1,3,5-triazine as a white solid having a melting point of 156ºC-157.5°C. NMR analysis of the product indicated the following: 'H NMR(CDCl3): δ 3.8(s,3H); 7.2-7.7(m,3H); 10.05(s, 1H) ppm.
This compound is referred to hereinafter as Compound 127.
Example LXII
In a manner similar to that employed in Example LXI, other compounds were prepared. The structures and analytical data for Compounds 128 through 131, which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table G below.
Figure imgf000404_0001
Figure imgf000405_0001
Example LXIII
Preparation of 2,4-dichloro-6- (5'-methylisoxazolyl-3'-amino)-1,3,5-triazine
Into a solution containing cyanuric chloride (5.0 grams, 0.03 mole) in acetone (100 milliliters) at a temperature of 0°C was added dropwise a solution containing 2,6-lutidine (3.15 milliliters. 0.03 mole) and 3-amino-5-methylisoxazole (2.66 grams. 0.03 mole) in acetone (50 milliliters) while maintaining the temperature below 5°C. After
2 hours of stirring, the reaction mixture was warmed to room temperature and then poured onto 200 milliliters of ice-water. The mixture was filtered, the solid dried and recrystallized from chloroform to afford 800 milligrams (0.003 mole) of 2,4-dichloro-6-(5'-methylisoxazolyl-3'-amino)-1,3,5-triazine as a solid having a melting point of 128°C-132°C. Elemental analysis of the product indicated the following:
Analysis: C7H5Cl2N5O
Calculated: C, 34.17; H, 2.05; N, 28.06
Found: C, 34.24; H, 2.11; N, 28.15
This compound is referred to hereinafter as Compound 132. Example LXIV
Preparation of 2, 4-dichloro-6- (2-pyridinylamino)-1,3,5-triazine
Into a solution containing cyanuric chloride (18.4 grams, 0.1 mole) in acetone (140 milliliters) and crushed ice-water (200 milliliters) was added dropwise 2-aminopyridine (9.4 grams, 0.1 mole) in acetone (68 milliliters) while maintaining the reaction temperature below 5°C. Sodium hydroxide (50 milliliters of a 2N solution, 0.1 mole) was then added keeping the temperature below 5°C and the pH below 8.0. The reaction mixture was filtered and chromatographed on silica gel to afford 590 milligrams (0.002 mole) of 2,4-dichloro-6-(2-pyridinylamino)-1,3,5-triazine as an orange solid having a melting point of 170°C-172ºC. Elemental analysis of the product indicated the following:
Analysis: C8H5Cl2N5
Calculated: C, 39.69; H, 2.08; N, 28.93 Found: C, 34.08; H, 1.47; N, 27.92
This compound is referred to hereinafter as Compound 133. Example LXV
Preparation of 2-benzoxazolylamino- 4,6-dichloro-1,3,5-triazine
Into a mixture containing 2-aminobenzoxazole (1.0 gram, 0.007 mole) and cyanuric chloride (1.38 grams, 0.007 mole) in acetone (12 milliliters) at a temperature of 0°C was added 5% sodium hydroxide solution (34 milliliters) at such a rate as to maintain the temperature of the reaction mixture below 10°C and to maintain the pH between 6.5 and 7.0. After the addition was completed, the reaction mixture was filtered and the solid (0.75 gram) recrystallized from chloroform to afford 100 milligrams (0.003 mole) of 2-benzoxazolylamino-4,6-dichloro-1,3,5-triazine as a white solid having a melting point greater than 250°C. Elemental . analysis of the product indicated the following:
Analysis: C10H5Cl2N5O
Calculated: C, 42.58; H, 1.79; N, 24.83
Found: C, 41.68; H, 1.78; N, 23.58
This compound is referred to hereinafter as Compound 134. Example LXVI
Preparation of 2,4-dichloro-6-(4'-quinazolinoxy) -1,3,5-triazine
Into a mixture containing 4-hydroxyquinazoline (5 grams, 0.03 mole) and cyanuric chloride (6.3 grams, 0.03 mole) in acetone (110 milliliters) was added 2% sodium hydroxide solution at such a rate as to maintain the temperature of the reaction mixture below 10°C and the pH between 6.5 and 7.0. After the addition was completed, the reaction mixture was allowed to warm to room temperature and stirred for about 16 hours. The reaction mixture was filtered, the solid placed in a Soxhlet extractor and extracted with refluxing chloroform. Evaporation of the solvent and chromatography on silica gel afforded 100 milligrams (0.0003 mole) of 2,4-dichloro-6-(4'-quinazolinoxy)-1,3,5-triazine as a solid having a melting point greater than 250°C. NMR analysis of the product indicated the following:
'H NMR (CDCl3): δ 7.2-8.2 ppm (5H. m), 8.5 ppm (1H,s)
This compound is referred to hereinafter as Compound 135. Example LXVII
Preparation of 2-(2-carbazolyloxy)- 4,6-dichloro-1,3,5-triazine
Into a mixture containing 2-hydroxycarbazole (3 grams, 0.02 mole) and cyanuric chloride (3 grams, 0.02 mole) in acetone (130 milliliters) at a temperature of 0°C was added 2% sodium hydroxide solution (130 milliliters) at such a rate as to maintain the temperature of the reaction mixture below 10°C and the pH between 6.5 and 7.0. After the addition was completed, the reaction mixture was stored in the refrigerator for about 16 hours and the solid product filtered and recrystallized from acetone. The solid was placed in a Soxhlet extractor, and extracted with refluxing chloroform for about 16 hours. Evaporation of the solvent afforded 3.75 grams (0.01 mole) of 2-(2-carbazolyloxy)-4,6-dichloro-1,3,5-triazine as a solid having a melting point of 249°C-256°C. Elemental analysis of the product indicated the following:
Analysis: C15H8Cl2N4O
Calculated: C, 54.40; H, 2.44; N, 16.92
Found: C, 53.38; H, 2.51; N, 16.50
This compound is referred to hereinafter as Compound 136. Example LXVIII
Preparation of 2,4-dichloro-6- [4-(2,3-dimethyl-1-phenyl-3-pyrazolin-5- one-amino)1-1,3,5-triazine
Into a solution containing cyanuric chloride (18.4 grams, 0.1 mole) in acetone (200 milliliters) and crushed ice-water (200 milliliters) was added dropwise 4-aminoantipyrine (20.3 grams. 0.1 mole) in acetone (180 milliliters) while maintaining the reaction temperature below 5°C. Sodium hydroxide (50 milliliters of a 2N solution, 0.1 mole) was then added keeping the temperature below 5°C, and the pH below 8.0. The reaction mixture was filtered, the filtrate evaporated to remove acetone and the residue continuously extracted with ether for a period of about 16 hours. The solvent was evaporated to afford 860 milligrams (0.003 mole) of 2,4-dichloro-6-[4-(2.3-dimethyl-1-phenyl-3-pyrazolin-5-one-amino)]-1, 3,5-triazine as a white solid having a melting point greater than 250°C. Elemental analysis of the product indicated the following:
Analysis : C14H12Cl2N2O
Calculated: C, 47.88; H, 3.45; N, 23.93 Found: C, 46.57; H, 3.49; N, 23.05
This compound is referred to hereinafter as Compound 137. Example LXIX
Preparation of 4,6-dichloro-2- (N-Phthalimido)-1,3,5-triazine
Into a solution containing 20.8 grams (0.1 mole) of cyanuric chloride in 100 milliliters of acetone was added a suspension of 20.8 grams (0.1 mole) of potassium phthalimide in 200 milliliters of acetone with cooling to a temperature of 0-4°C. The resulting mixture was stirred at 0-4ºC for 3 hours and then stirred at room temperature for about 16 hours. The mixture was filtered and the filtrate poured into ice-water with trituration to effect precipitation. The mixture was filtered and the solid dried in vacuo to give 17 grams of crude product. This crude product was recrystallized from CH2Cl2-hexane to give 4.5 grams (0.02 mole) of 4,6-dichloro-2-(N-phthalimido)-1,3,5-triazine having a melting point of 176°C-177°C Elemental analysis of the product indicated the following:
Analysis: C11H4Cl2N4O2
Calculated: C, 44.90; H, 1.36 Found: C, 45.05; H, 1.97
This compound is referred to hereinafter as Compound 138. Example LXX
Preparation of 4, 6-dichloro-2- (N-3,4,5,6-tetrachlorophthalimido)-1,3,5-triazine
Into a suspension containing 4.02 grams (0.04 mole) of 35% by weight KH in oil was added 100 milliliters of tetrahydrofuran and a solution containing 3,4,5,6-tetrachlorophthalimide (10.0 grams. 0.03 mole) in tetrahydrofuran at a temperature of 4°C. The mixture was stirred at room temperature for 30 minutes, cooled to 0°C and a solution containing 6.47 grams (0.04 mole) of cyanuric chloride in 150 milliliters of dry tetrahydrofuran was added. The mixture was stirred at room temperature for about 16 hours, filtered and the filtrate poured onto ice-water. The precipitate was filtered to give 20 grams of crude product. This material was extracted with hot CH2Cl2. The methylene chloride solution was cooled to room temperature and hexane added to crystallize the product. Filtration gave 700 milligrams (0.002 mole) of 4,6-dichloro-2-(N-3,4,5,6-tetrachlorophthalimido)-1,3,5-triazine as a while solid having a melting point of 298ºC-300°C. IR analysis of the product indicated the following:
IR(KBr) 1745, 1510, 1400, 1370, 1300 and 1235 cm-1.
This compound is referred to hereinafter as Compound 139. Example LXXI
Preparation of 2-(4',6'-dichloro-1', 3'.5'-triazin-2'-yl)-1,2-benzisothiazol- 3(2H)one 1,1-dioxide
Into a solution containing 100 grams (0.054 mole) of cyanuric chloride in 200 milliliters of acetone was added a suspension containing 10 grams (0.054 mole) of saccharin in 100 milliliters of acetone. The mixture turned homogeneous after several minutes, and 5.5 milliliters (0.054 mole) of 2,6-lutidine were added followed by stirring at room temperature under a nitrogen atmosphere for about 16 hours. The suspension was then filtered, the filtrate evaporated, and the residue was partially crystallized from CH2Cl2-hexane. This solid was filtered and the filtrate evaporated to give a residue which was recrystallized from CH2Cl2- hexane to give 2.0 grams (0.006 mole) of 2-(4', 6'-dichloro-1',3',5'-triazin-2,-yl)-1,2-benzisothiazol -3(2H)one 1,1-dioxide. Elemental analysis of the product indicated the following:
Analysis: C10H4O3Cl2N4S
Calculated: C, 38.60; H, 1.30; N, 18.01;
Cl, 22.79 Found: C, 36.59; H, 1.43; N, 16.27;
Cl, 20.71
This compound is referred to hereinafter as Compound 140. Example LXXII
Preparation of 2,4-dichloro-6- trimethylsilylethynyl-1,3,5-triazine
Ethylmagnesium bromide (35.4 milliliters of 2 M tetrahydrofuran solution) was added dropwise to a solution of trimethylsilylacetylene (14.4 milliliters. 0.1 mole) in tetrahydrofuran (80 milliliters) at a temperature of -60°C. The solution was allowed to warm to room temperature, stirred for 2 hours and then heated at 40°C for 1 hour. The solution was cooled to room temperature and then added dropwise to a solution of cyanuric chloride (12 grams. 0.07 mole) in tetrahydrofuran (65 milliliters). After 1 hour at room temperature, the solvent was evaporated and the residue extracted with ether. The ether was evaporated and the residue chromatographed on silica gel to afford 1.2 grams (0.005 mole) of 2,4-dichloro-6-trimethylsilylethynyl-1,3,5-triazine as a brown oil. Elemental analysis of the product indicated the following:
Analysis: C8H9Cl2N3Si1
Calculated: C, 39.03; H, 3.69;N, 17.07 Found: C, 39.67; H, 3.90; N, 15.97
The compound is referred to hereinafter as Compound 141. Example LXXIII
Preparation of 2,4-dichloro-6- ethoxyethynyl-1,3,5-triazine
Into ethylmagnesium bromide (21.0 milliliters of a 2M solution in tetrahydrofuran) was added dropwise a solution of ethoxyacetylene (3.0 grams. 0.04 mole) in tetrahydrofuran (21 milliliters) at a temperature of 0°C. After the addition was complete, the reaction mixture was heated to 40ºC for 1 hour, cooled to 0ºC and then added dropwise to a solution of cyanuric chloride (7.9 grams, 0.04 mole) in tetrahydrofuran (21 milliliters). The reaction mixture was stirred for about 16 hours, the solvent evaporated, and the residue extracted with ether. The ether was evaporated and the residue chromatographed on silica gel to afford 1.5 grams (0.007 mole) of 2,4-dichloro-6-ethoxyethynyl-1,3,5-triazine as an orange oil. NMR analysis of the product indicated the following: 'H NMR(CDCl3): δ 1.4(t,3H); 4.55(q,2H) ppm.
This compound is referred to hereinafter as Compound 142. Example LXXIV
Preparation of 2,4-dichloro-6- methylsulfonamido-1,3,5-triazine
Into a mixture containing methanesulfonamide (9.5 grams. 0.1 mole) and sodium hydroxide (4 grams. 0.1 mole) in water (0.5 liter) at a temperature of 25°C was added a solution containing cyanuric chloride (18.4 grams, 0.1 mole) in acetone (100 milliliters). After the addition was completed, sodium hydroxide (4 grams. 0.1 mole) in water (25 milliliters) was added dropwise while maintaining the pH of the reaction mixture below 8.0. The reaction mixture was placed in the refrigerator for about 16 hours, warmed to room temperature and filtered to afford a white solid. Recrystallization from chloroform gave 400 milligrams (0.002 mole) of 2,4-dichloro-6-methylsulfonamido-1,3,5-triazine as a white solid having a melting point of 204°C-206°C. Elemental analysis of the product indicated the following:
Analysis: C4H4Cl2N4O2S
Calculated: C, 19.76; H, 1.66; N, 23.05.
Found: C, 19.48; H, 1.68; N, 22.44.
This compound is referred to hereinafter as Compound 143. Example LXXV
Preparation of 2,4-dichloro-6- (1'-piperidinoamino)-1,3,5-triazine
Into a solution containing cyanuric chloride (5.0 grams, 0.03 mole) in acetone (120 milliliters) at a temperature of 0°C was added dropwise a solution containing 2.6-lutidine (3.15 milliliters, 0.03 mole) and N-aminopiperidine (2.7 grams. 0.03 mole) in acetone (21 milliliters) while maintaining the temperature below 5°C. After 2 hours of stirring, the reaction mixture was warmed to room temperature and stirred for 1 hour. The reaction mixture was then filtered and. the filtrate evaporated. The residue was chromatographed on silica gel to afford 620 milligrams (0.002 mole) of 2,4-dichloro-6-(1'-piperidinoamino)-1,3,5-triazine as a yellow solid having a melting point of 114°C-117°C. Elemental analysis of the product indicated the following:
Analysis: C8H11Cl2N5
Calculated: C, 38.72; H, 4.47; N, 28.23. Found: C, 37.31; H, 4.51; N, 26.75.
This compound is referred to hereinafter as Compound 144. Example LXXVI
Preparation of 2,4-bis- (dimethylamino)-6-chloro-1,3,5-triazine
Into a solution containing cyanuric chloride (92.2 grams. 0.5 mole) dissolved in acetone (350 milliliters) and cooled to a temperature of -30°C was added liquid dimethylamine (90 grams, 2.0 moles) while maintaining the reaction temperature below -20°C. After reaction mixture ceased stirring, the internal temperature rose to 5°C. The reaction mixture was then poured onto crushed ice (2 kilograms) and the acetone evaporated by blowing air over the surface while maintaining the mixture at 0°C. After filtration, the solid (124 grams) was recrystallized from pentane and chromatographed on silica gel to afford 400 milligrams (0.002 mole) of 2,4-bis(dimethylamino)-6-chloro-1,3,5-triazine as a yellow solid having a melting point of 62ºC-64°C. Elemental analysis of the product indicated the following:
Analysis: C7H12ClN5
Calculated: C, 41.69; H, 6.00; N, 34.73
Found: C, 41.32; N, 5.94; N, 35.18
This compound is referred to hereinafter as Compound 145. Example LXXVII
Preparation of 2,4,-dichloro-6- dimethylamino-1,3,5-triazine
Into a solution containing cyanuric chloride (92.2 grams. 0.5 mole) dissolved in acetone (380 milliliters) and cooled to a temperature of -30°C was added dropwise 40% aqueous dimethylamine (79 grams, 0.7 mole) while maintaining the reaction temperature below -20°C. After addition was completed, the reaction mixture was stirred at -10°C for 30 minutes The reaction mixture was poured onto crushed ice (2 kilograms) and the acetone evaporated by blowing air over the surface while maintaining the mixture at 0°C. After filtration, the solid was recrystallized from pentane to afford 59.0 grams (0.3 mole) of 2,4-dichloro-6-dimethylamino-1,3,5-triazine as a white solid having a melting point of 111.5°C-115.5°C. Elemental analysis of the product indicated the following:
Analysis: C5H6Cl2N4
Calculated: C, 31.11; H, 3.13; N, 29.03
Found: C, 31.06; H, 3.06; N, 29.46
This compound is referred to hereinafter as Compound 146. Example LXXVIII
Preparation of 2,4-dichloro-6- (1-morpholinyl)-1,3,5-triazine
Into a solution containing cyanuric chloride (18.4 grams. 0.1 mole) in acetone (120 milliliters) and crushed ice-water (200 milliliters) was added dropwise morpholine (17.4 grams, 0.1 mole) while maintaining the reaction temperature below 5°C. To this mixture was added a sodium hydroxide solution (25 milliliters of 2N solution) while keeping the temperature below 5°C and the pH below 8.0. The reaction mixture was filtered and the separated solid recrystallized from ether to afford 8.0 grams (0.03 mole) of 2,4-dichloro-6-(1-morpholinyl)-1,3,5-triazine as a white solid having a melting point of 154ºC-l57°C. Elemental analysis of the product indicated the following:
Analysis: C7H8Cl2N4O Calculated: C, 35.76; H, 3.43; N, 23.84
Found: C, 35.58; H. 3.60; N, 23.83
This compound is referred to hereinafter as Compound
147.
Example LXXIX
In a manner similar to that employed in Example LXXVIII. other compounds were prepared. The structures and analytical data for Compounds 148 and 149. which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table H below.
Figure imgf000423_0001
Example LXXX
Preparation of 2-bis(chloromethyl) amino-4,6-dichloro-1,3,5-triazine
2,4-Dichloro-6-dimethylamino-1,3,5-triazine (18.0 grams, 0.09 mole) prepared in Example LXXVII was heated to a temperature of 130°C. chlorine gas introduced and the solution irradiated with ultraviolet light for a period of 5 hours. The resulting residue was chromatographed on silica gel to afford 300 milligrams (0.001 mole) of
2-bis(chloromethyl)amino-4-6-dichloro-1,3,5-triazine as an oil. Elemental analysis of the product indicated the following:
Analysis: C5H4CI4N4
Calculated: C, 22.92; H, 1.54; N, 21.39 Found: C, 23.10; H, 1.87; N, 21.93
This compound is referred to hereinafter as Compound 150.
Example LXXXI
Preparation of 2,2'-[1,2-phenylenebis(oxy)]- bis[4,6-dichloro-1,3,5-triazine]
In a manner similar to that employed in Example LIV, cyanuric chloride was reacted with 1,2-dihydroxybenzene in the presence of 2,6-lutidine as an acid acceptor to give 2,2'-[1,2-phenylenebis (oxy)]-bis[4,6-dichloro-1,3,5-triazine] having a melting point of 154ºC-156°C. Elemental analysis of the product indicated the following:
Analysis: C12H4Cl4N6O2
Calculated: C, 35.50; H, 0.99; N, 20.70
Found: C, 35.60; H, 1.29; N, 20.68
This compound is referred to hereinafter as Compound 151.
Example LXXXII
Preparation of 2,4-dibromo-6-isopropoxy- 1,3,5-triazine
Part A. Preparation of 2,4-dichloro- 6-isopropoxy-1,3,5-triazine Into a stirred solution containing 20.0 grams (0.108 mole) of cyanuric chloride in 150 milliliters of acetone was added 12.6 milliliters (0.12 mole) of 2.6-lutidine dropwise at temperature of -70°C. 2- Propanol (8.3 milliliters. 0.11 mole) was added and The resulting mixture stirred under a nitrogen atmosphere at room temperature for about 16 hours. The reaction mixture was then evaporated free of solvent and the residue partitioned between ethyl ether and water. The organic layer was dried (anhydrous Na2SO4), evaporated and the residue distilled in vacuo to give 2.0 grams (0.01 mole) of 2,4-dichloro-6-isopropoxy-1,3,5-triazine as an oil having a boiling point of 152ºC- 155°C/42 millimeters Hg.
Part B. Preparation of 2,4-dibromo-6- isopropoxy-1,3,5-triazine
2,4-Dichloro-6-isopropoxy-1,3,5-triazine prepared in Part A was treated with gaseous hydrogen bromide in a methylene chloride solution at a temperature of 25ºC by employing a procedure similar to that described in Example XIX to give 2,4,-dibromo-6-isopropoxy-1,3,5-triazine as an unstable solid. Elemental analysis of the product indicated the following:
Analysis: C6H7Br2N3O
Calculated: C, 24.24; H, 2.36; N, 14.14;
Br, 53.87 Found: C, 21.14; H, 2.83; N,
13.89; Br, 53.88
This compound is referred to hereinafter as Compound 152.
Example LXXXIII
Preparation of 5-(3',5'-dichlorophenoxy)- 3,6-dichloro-1,2,4-triazine
Part A. Preparation of 3,5,6-trichloro- 1,2,4-triazine
A mixture containing 6-azauracil (50 grams. 0.44 mole), bromine (49.8 milliliters, 1.0 mole), and water (625 milliliters) was stirred with a magnetic stirrer for 27 hours. The mixture was filtered to yield a white powder. Concentration of the filtrate gave additional product that was combined with the first. The white solid was recrystallized from water and dried to give 53.4 grams (0.33 mole) of 5-bromo-6-azauracil having a melting point of 234ºC-237ºc
Into 14.4 grams (0.08 mole) of 5-bromo-6-azauracil prepared above in 299.5 milliliters (3.4 mole) of phosphorus oxychloride was added 30.0 grams (0.14 mole) of phosphorus pentachloride and 30 milliliters (0.19 mole) of N,N-diethylaniline. The mixture was magnetically stirred and heated under reflux for 2 hours and allowed to stand at room temperature for 24 hours. The excess solvent was removed under reduced pressure and the residue extracted with eight 200 milliliters portions of dry ether. The ether was removed and the residue distilled at 70°C/0.007 millimeters to give 8.77 grams (0.05 mole) of 3,5,6-trichloro-1,2,4-triazine having a melting point of 56°C-58ºC. Part B. Preparation of 5-(3',5'-dichlorophenoxy) -3,6-dichloro-1,2,4-triazine
Into a solution containing 1.84 grams (0.01 mole) of 3,5,6-trichloro-1,2,4-triazine prepared in Part A in 50 milliliters of acetone was added, with cooling and stirring, 1.07 grams (0.01 mole) of 2,6-lutidine and 1.63 grams (0.01 mole) of 3,5-dichlorophenol dissolved in 10 milliliters of acetone at such a rate that the reaction temperature remained at 0-5°C. The reaction mixture was magnetically stirred for 2 hours and allowed to warm to room temperature. The precipitated 2,6-lutidine hydrochloride was filtered off and washed in 50 milliliters of acetone. The acetone solution was poured onto about 100 grams of ice and the product that precipitated was collected and washed with 20 milliliters of cold 10% aqueous NaOH and 10 milliliters of cold water. The solid was dried and crystallized from hexane to give 2.3 grams (0.007 mole) of 5-(3',5'-dichlorophenoxy)-3,6-dichloro1,2,4-triazine as a white solid having a melting point of 130ºC-132ºC. Elemental analysis of the product indicated the following:
Analysis: C9H3Cl4N3O
Calculated: C, 34.76; H, 0.97; N, 13.51
Found: C, 34.64; H. 0.93; N, 13.69
This compound is referred to hereinafter as Compound 153. Example LXXXIX
In a manner similar to that employed in Example LXXXVIII, other compounds were prepared. The structures and analytical data for Compounds 154 through 156, which compounds were used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table I below.
Figure imgf000430_0001
Example XC
Preparation of 5-(2',4'-dichlorophenoxy)- 3,6-dichloro-1,2,4-triazine
3,5,6-Trichloro-1,2,4-triazine and 2,4-dichlorophenol were reacted in an acetone solution employing quinaldine as the acid acceptor in a manner similar to that employed in Example III to give 3.0 grams (0.01 mole) of 5-(2',4"-dichlorophenoxy)-3,6-dichloro-1,2,4-triazine having a melting point of 90°C-93ºC after recrystallization from hexane. Infrared analysis of the product indicated the following: IR (KBr) 3090. 1530. 1505, 1470, 1400, 1295, 1235, 1205, 1100, 1050, 985, 865, 830, 750 cm-1.
This compound is referred to hereinafter as Compound 157.
Example XCI
In a manner similar to that employed in Example XC, other compounds were prepared. The structure and analytical data for Compounds 158 through 160. which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table J below.
Figure imgf000432_0001
Example XCII
Preparation of 2,6-dichlorobenzaldehyde O-(3,6-dichloro-1,2,4-triazin-4-yl)oxime
In a manner similar to that employed in Example XXXVI, 3,5,6-trichloro-1,2,4-triazine was reacted with 2,6-dichlorobenzaldoxime to give 0.93 gram (0.003 mole) of 2.6-dichlorobenzaldehyde O-(3,6-dichloro-1,2,4-triazin-4-yl)oxime having a melting point of 103ºC-105°C. Elemental analysis of the product indicated the following:
Analysis: C10H4Cl4N4O
Calculated: C, 35.54; H, 1.19; N, 16.58 Found: C, 35.76; H, 1.60; N, 17.04
This compound is referred to hereinafter as Compound 161.
Example XCIII
Preparation of 3-chloro-6- (2',4'-dichlorophenoxy)pyridazine
A mixture containing 5.96 grams (0.04 mole) of 3,6-dichloropyridazine, 6.52 grams (0.04 mole) of 2,4-dichlorophenol, and 5.80 grams (0.04 mole) of K2CO3 in 200 milliliters of acetone was heated on a steam bath for a period of 2 hours. The solvent was removed and the residue washed with 100 milliliters of 10% aqueous NaOH and then 100 milliliters of water. The crude solid was crystallized from hexane to give a total of 1.6 grams (0.006 mole) of 3-chloro-6-(2',4'-dichlorophenoxy)pyridazine as a white solid having a melting point of 89°C-91°C. Elemental analysis of the product indicated the following:
Analysis: C10H5Cl3N2O
Calculated: C, 43.59; H, 1.83; N, 10.17
Found: C, 43.59; H, 1.91; N, 10.06
This compound is referred to hereinafter as Compound 162
Example XCIV
In a manner similar to that employed in Example XCIII, other compounds were prepared. The structures and analytical data for Compound 163, which compound is used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table K below.
Figure imgf000435_0001
Example XCV
Preparation of tris(4.6-dichloro- 1,3,5-triazin-2-yl)amine
In the procedure employed in Example LVI for the preparation of bis(4,6-dichloro-1,3,5-triazin-2-yl)amine. a solid precipitate was isolated by filtration to give tris(4,6-dichloro-1,3,5-triazin-2-yl)amine as a by-product having a melting point of greater than 360ºC (dec). Elemental analysis of the product indicated the following:
Analysis: C9Cl6N10
Calculated: C, 23.45; H, 0.00, N, 30.39 Found: C, 21.85; H, 1.18; N, 33.65
This compound is referred to hereinafter as Compound 164.
Example XCVI
In a manner similar to that employed in Example XCIII, other compounds were prepaxed. The structures and analytical data for Compound 165, which compound is used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table L below.
Figure imgf000437_0001
Example XCVII
Preparation of 3-chloro-6- (3'-chlorophenoxy)pyridazine
Into a solution containing 1.93 grams (0.015 mole) of 3-chlorophenol and 1.5 grams (0.005 mole) of tetrabutylammonium bromide in 24 milliliters of 1.25 N aqueous sodium hydroxide was added 2.23 grams (0.015 mole) of 3,6-dichloropyridazine dissolved in 50 milliliters of toluene. The mixture was heated to a temperature of 50°C and stirred for 3 hours. The organic layer was separated, washed with dilute- NaOH solution and water, dried over MgSO4 and evaporated. The residue obtained was crystallized from hexane to give 1.55 grams (0.006 mole) of 3-chloro-6-(3'-chloro-phenoxy)pyridazine as a white solid having a melting point of 85ºC-88°C. Elemental analysis of the product indicated the following:
Analysis : C10H6Cl2N2O
Calculated: C, 49.82; H, 2.51; N, 11.62 Found: C, 49.87; H, 2.48; N, 11.65
This compound is referred to hereinafter as Compound 166. Example XCVIII
Preparation of 4-(4'-nitrophenoxy) -2,5,6-trichloropyrimidine
In a manner similar to that employed in Example I, 2,4,5,6-tetrachloropyrimidine and 4-nitrophenol were reacted in acetone solution employing 2,6-lutidine as the acceptor to give 0.8 gram (0.002 mole) of 4-(4'-nitrophenoxy)-2,5,6-trichloropyrimidine having a melting point of 114ºC-116°C following vacuum sublimation and two recrystallizations from hexane. Elemental analysis of the product indicated the following:
Analysis: C10H4Cl3N3O3
Calculated: C, 37.47; H, 1.26; N, 13.11;
Cl, 33.18
Found: C, 36.89; H, 1.52; N, 13.00;
Cl, 32.79
This compound is referred to hereinafter as Compound 167.
Example XCIX
In a manner similar to that employed in Example XCVIII, other compounds were prepared. The structures and analytical data for Compounds 168 and 169. which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table M below. .
Figure imgf000440_0001
Example C
Preparation of 2-(2',4'-dichlorophenoxy) pentachlorocyclotriphosphazene
Into a solution containing 10.8 grams (0.03 mole) of phosphonitrilic chloride trimer in 50 milliliters of acetone at a temperature of -60°C and under nitrogen atmosphere was added dropwise 3.1 milliliters (0.03 mole) of 2,6-lutidine in 10 milliliters of acetone and 5.0 grams (0.03 mole) of 2,4-dichlorophenol in 40 milliliters of acetone. The reaction mixture was allowed to warm to room temperature, stirred for about 16 hours, filtered and the filtrate poured into ice water. The solid (6.8 grams) was collected by filtration, and sublimation removed the unconverted 2,4-dichlorophenol. The pink semi-solid remaining in the sublimer was collected to give 0.9 gram (0.002 mole) of 2-(2',4'-dichlorophenoxy)pentachlorocyclotriphosphazene. NMR analysis of the product indicated the following: 'H NMR (CDCl3): δ 7.20-7.55 ppm (m, aromatic protons).
This compound is referred to hereinafter as Compound 170. Example CI
Preparation of 2,4-dichloro-6- (2'.4'-dichlorophenoxy)hexahydro-1,3,5-triazine
Into a suspension containing 340 milligrams (0.001 mole) of 2,4-dichloro-6-(2'4'-dichlorophenoxy)-1,3,5-triazine in 50 milliliters of anhydrous ethyl ether was added 400 milligrams (0.01 mole) of sodium borohydride and 5 milliliters of methanol in portions. The mixture was stirred for 5 minutes and an additional 420 milligrams (0.01 mole) of sodium borohydride was added. After the mixture was stirred for 15 minutes. 150 milliliters of ether was added and the mixture then partitioned between ether and water. The organic layer was dried (Na2SO4) and evaporated to give 340 milligrams (0.001 mole) of 2,4-dichloro-6-(2',4'-dichlorophenoxy)hexahydro-1,3,5-triazine as a white unstable solid. NMR analysis of the product indicated the following:
13C NMR(CD3CN/D2O): δ 118.53, 121.86, 124.87, 125.71, 128.82, 129.5, 130.09 and 130.93 ppm.
This compound is referred to hereinafter as Compound 171. Example CII
Preparation of 2,4-dichloro-6- [4-(4-ethoxyphenylazo)-1-naphthoxy]- 1,3,5-triazine
In a manner similar to that employed in Example LIII. 2,4-dichloro-6-[4-(4-ethoxyphenylazo)-1-naphthoxy]-1,3,5-triazine was prepared having a melting point of 173ºC-177°C. Elemental analysis of the product indicated the following:
Analysis: C21H15Cl2N5O2
Calculated: C, 57.29; H, 3.43; N, 15.90
Found: C, 57.52; H, 4.08; N, 15.66
This compound is referred to hereinafter as Compound
172.
Example CIII Preparation of 2,4-dichloro-6-(2-methoxyphenoxy)- 1,3,5-triazine In a manner similar to that employed in Part B of Example XXII, cyanuric chloride was reacted with 2-methoxyphenol in the presence of 2,6-lutidine as an acid acceptor to give 2,4-dichloro-6-(2-methoxyphenoxy)-1,3,5-triazine having a melting point of 93°C-94.5°C. Elemental analysis of the product indicated the followi:ng: Analysis: C10H7Cl2N3O2
Calculated: C, 44.14; H, 2.59; N, 15.44
Found: C, 43.99; H, 3.00; N, 15.27
This compound is referred to hereinafter as Compound 173.
Example CIV Preparation of 2,4-dichloro-6-(2-benzyloxyphenoxy)- 1,3,5-triazine In a manner similar to that employed in Part B of Example XXII, cyanuric chloride was reacted with 2-benzyloxyphenoi-in the presence of 2,6-lutidine as an acid acceptor to give 2,4-dichloro-6-(2-benzyloxyphenoxy)-1,3,5-triazine having a melting point of 92°C-94ºC. Elemental analysis of the product indicated the following:
Analysis: C16H11Cl2N3O2
Calculated: C, 55.19; H, 3.18; N, 12.07
Found: C, 55.59; H, 3.19; N, 11.76
This compound is referred to hereinafter as Compound
174.
Example CV
Preparation of 2,4-dichloro-6-[4-(1-methyl- 1-[4-oropoxyphenyl]ethyl)]phenoxy-1,3,5-triazine
Part A. Preparation of 4-[ 1methyl-1-(4- propoxyphenyl)ethyl]phenol
A mixture of Bisphenol A (5.0 grams, 0.02 mole), potassium carbonate (3.04 grams, 0.02 mole) and 100 milliliters of acetophenone was stirred and heated at a temperature of 150°C for a period of 2 hours. After cooling to room temperature, 1-iodopropane (3.22 milliliters, 0.03 mole) was added and the mixture was then stirred and heated at a temperature of 100°C for a period of about 16 hours. The reaction mixture was then allowed to cool and the solid removed by filtration. The acetophenone was removed by distillation under reduced pressure and the residue purified by flash chromatography (5% ethyl acetate/hexane eluant) to give 2.12 grams (0.008 mole) of 4-[1-methyl-1-(4-propoxyphenyl)-ethyl]phenol. NMR analysis of the phenol intermediate indicated the following: 'H NMR (CDCl3): δ 0.80-1.91 (m, 11H) , 3.90 (t, 2H, J = 7HZ), 5.15 (s, H), 6.57-7.21 (m, 8H) ppm.
Part B. Preparation of 2,4-dichloro-6-[4- (1-methyl-1-[4-propoxyphenyl]- ethyl)]phenoxy-1,3,5-triazine In a manner similar to that employed in Part B of Example XXII, cyanuric chloride was reacted with 4-[1-methyl-1-(4-propoxyphenyl)-ethyl]phenol prepared in Part A above in the presence of 2,6-lutidine as an acid acceptor to give 2,4-dichloro-6-[4-(1-methyl-1-[4-propoxyphenyl]-ethyl)]phenoxy-1,3,5-triazine as an oil. Elemental analysis of the product indicated the following:
Analysis: C2lH21Cl2N3O2
Calculated: C, 60.30; H, 5.06; N, 10.04
Found: C, 59.62; H, 5.06; N, 10.84 This compound is referred to hereinafter as Compound 175.
Example CVI Preparation of 2,4-dichloro-6-[4-(1-methyl-1- [4-methoxyphenyl]ethyl)]phenoxy-1,3,5-triazine
Part A. Preparation of 4-[1-methyl-1-(4-methoxyphenyl)ethyl]phenol
In a manner similar to that employed in Part A of Example CV, Bisphenol A was reacted with methyl iodide in acetone solution and in the presence of potassium carbonate as an acid acceptor to give 4-[1-methyl-1-(4-methoxyphenyl)ethyl]-phenol. NMR analysis of the phenol intermediate indicated the following: 'H NMR (CDCl3):δ 1.63 (s, 6H), 3.77 (s, 3H), 5.62 (s, H), 6.55-7.27 (m, 8H) ppm.
Part B. Preparation of 2,4-dichloro-6-[4-(1- methyl-1-[4-methoxyphenyl]ethyl)]- phenoxy-1,3,5-triazine In a manner similar to that employed in Part B of Example XXII, cyanuric chloride was reacted with 4-[1-methyl-1-(4-methoxyphenyl)-ethyl]phenol prepared in Part A above in the presence of 2,6-lutidine as an acid acceptor to give 2,4-dichloro-6-[4-(1-methyl-l-[4-methoxyphenyl]-ethyl)]phenoxy-1,3,5-triazine having a melting point of 108°C-111°C. Elemental analysis of the product indicated the following: Analysis: C19H17Cl2N3O2
Calculated: C, 58.47; H, 4.39; N, 10.77 Found: C, 58.35; H, 4.40; N, 10.76
This compound is referred to hereinafter as Compound
176.
Example CVII
Preparation of 2,4-dichloro-6-[4-(1-methyl-1- [4-benzyloxyphenyl]ethyl)]-phenoxy-1,3,5-triazine
Part A. Preparation of 4-[1-methyl-1-(4-benzyloxyphenyl)ethyl]phenol
In a manner similar to that employed in Part A of Example CV, Bisphenol A was reacted with benzyl chloride in acetone solution in the presence of potassium carbonate as an acid acceptor to give 4-[1-methyl-1-(4-benzyloxyphenyl)ethyl]phenol. NMR analysis of the phenol intermediate indicated the following: 'H NMR (CDCl3) :δ 1.60 (s, 6H), 4.57 (s, H), 5.00 (s, 2H), 6.56-7.48 (m, 8H) ppm.
Part B. Preparation of 2,4-dichloro-6-[4- (1-methyl-1-[4-benzyloxyphenyl]-ethyl)]- phenoxy-1,3,5-triazine In a manner similar to that employed in Part B of Example XXII, cyanuric chloride was reacted with 4-[1-methyl-1-(4-benzyloxyphenyl)-ethyl]phenol prepared in Part A above in the presence of 2,6-lutidine as an acid acceptor to give 2,4-dichloro-6-[4-(1-methyl-1-[4-benzyloxyphenyl]-ethyl)]phenoxy-1,3,5-triazine having a melting point of 117.5ºC-119°C. Elemental analysis of the product indicated the following:
Analysis: C25H21Cl2N3O2
Calculated: C, 64.39; H, 4.54; N, 9.01
Found: C, 64.09; H, 4.59; N, 8.87
This compound is referred to hereinafter as Compound
177.
Example CVIII Preparation of 2,4-dichloro-6-(2-n-butyloxyphenoxy)- 1,3,5-triazine
Part A. Preparation of 2-(n-butyloxy)phenol
In a manner similar to that employed in Part A of Example XXII, catechol was reacted with 1-bromobutane in the presence of sodium hydroxide as an acid acceptor to give 2-(n-butyloxy)phenol. NMR analysis of the phenol intermediate indicated the following: 'H NMR (CDCl3):δ 0.73-1.95 (m, 7H), 3.63-4.08 (t, 2H), 6.02-7.32 (m, 4H) ppm.
Part B. Preparation of 2,4-dichloro-6-(2-n-butyloxy- phenoxy)-1,3,5-triazine
In a manner similar to that employed in Part B of Example XXII, cyanuric chloride was reacted with 2-(n-butyloxy)phenol prepared in Part A above the presence of 2,6-lutidine as an acid acceptor to give 2,4-dichloro-6-(2-n-butyloxyphenoxy)-1,3,5-triazine as an oil. Elemental analysis of the product indicated the following: Analysis: C13H13Cl2N3O2
Calculated: C, 49.70; H, 4.17; N, 13.37 Found: C, 50.82; H, 4.69; N, 12.98 This compound is referred to hereinafter as Compound
178.
Example CIX In a manner similar to that employed in Example CVIII, other compounds were prepared. The structures and analytical data for Compounds 179 through 184, which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table N below.
Figure imgf000450_0001
Figure imgf000451_0001
Example CX
Preparation of 2,4-dichloro-6-[4-(4-benzyloxyphenylthio)]phenoxy-1,3,5-triazine
Part A. Preparation of 4-[(4-benzyloxyphenylthio)]- phenol
A mixture of 5.0 grams (0.02 mole) of 4,4'-thiobisphenol. 3.79 grams (0.03 mole) of potassium carbonate and 75 milliliters of acetone was heated under reflux for a period of 2 hours. After cooling to room temperature, 4.35 grams (0.03 mole) of benzyl chloride added dropwise to the reaction mixture which was then heated under reflux for a period of 16 hours. The reaction mixture was then cooled to room temperature and filtered through Celite to remove solid materials. The filtrate was concentrated in vacuo and the residue purified by flash chromatography to give 2.82 grams (0.01 mole) of 4-[(4-benzyloxy- phenylthio)]phenol. NMR analysis of the phenol intermediate indicated the following: 'H NMR (CDCl3):δ 4.98 (s, H), 5.08 (s, 2H), 6.65-7.50 (m, 13H) ppm.
Part B. Preparation of 2,4-dichloro-6-[4-(4- benzyloxyphenylthio)Iphenoxy-1,3,5-triazine In a manner similar to that employed in Part B of Example XXII, cyanuric chloride was reacted with 4-[(4-benzyloxyphenylthio)]phenol prepared in Part A above in the presence of 2,6-lutidine as an acid acceptor to give 2,4-dichloro-6-[4-(4-benzyloxyphenylthio)]phenoxy-1,3,5- triazine having a melting point of 119ºC-120ºC. Elemental analysis of the product indicated the following:
Analysis: C22H15Cl2N3O2S Calculated: C, 57.90; H, 3.31; N, 9.20 Found: C, 58.49; H, 3.60; N, 8.94
This compound is referred to hereinafter as Compound
185.
Example CXI In a manner similar to that employed in Example CX, other compounds were prepared. The structures and analytical data for Compounds 186 and 187, which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table O below.
Figure imgf000454_0001
Example CXI I Preparation of 2-chloro-4-methyl-6-[4-(1-methyl-1- [4-methoxyphenyl]ethyl)]-phenoxy-1,3,5-triazine To a stirred solution of 0.72 gram (0.002 mole) of 2,4-dichloro-6-[4-(1-methyl-1-[4-methoxy-phenyl]ethyl)]phenoxy-1,3,5-triazine prepared in Example CVI in 50 milliliters of tetrahydrofuran was slowly added 2.04 milliliters (0.006 mole) of 2.7 M methylmagnesium bromide in ethyl ether solution while cooling the mixture in an ice bath. After this period, the reaction mixture was allowed to warm to room temperature and then stirred for a period of 15 hours. The solvents were removed by vacuum evaporation and the residue purified by flash chromatography (3% ethyl acetate in hexane eluant) to give 0.43 grams (0.001 mole) of 2-chloro-4-methyl-6-[4-(1-methyl-1-[4-methoxyphenyl]ethyl)]phenoxy-1,3,5-triazine as pale yellow crystals having a melting point of 65.0ºC-67.5°C. Elemental analysis of the product indicated the following:
Analysis: C20H20ClN3O2
Calculated: C, 64.95; H, 5.45; N, 11.36
Found: C, 64.58; H, 5.57; N, 11.25
This compound is referred to hereinafter as Compound
188. Example CXIII
Preparation of 2,4-dichloro-6-[4-(chlorophenylsulfonyl)]phenoxy-1,3,5-triazine
Part A. Preparation of 4-chlorophenyl 4'-hydroxyphenyl sulfone
To a stirred solution of 28.7 grams (0.1 mole) of bis (4-chlorophenyl) sulfone in 100 milliliters of dimethylsulfoxide was added a solution of 13.1 grams (0.23 mole) of potassium hydroxide in 15 milliliters of water over a 10 minute period while heating the reaction mixture at a temperature of 40°C. The reaction mixture was then heated at a temperature of 105ºC for a period of 5 hours, cooled to room temperature and poured into 300 milliliters of water. A white, milky precipitate was filtered off and the filtrate acidified with HCl. The aqueous solution was extracted with ether (3 x 100 milliliters) and the combined ether layers washed with 10% aqueous NaOH (2 x 50 milliliters). The combined basic layers were acidified with HCl and extracted with ether (2 x 50 milliliters). Evaporation of ether gave 19.21 grams (0.08 mole) of 4-chlorophenyl 4'-hydroxyphenyl sulfone having a melting point of 143.0ºC-146.0ºC.
Part B. Preparation of 2,4-dichloro-6-[4-(4-chlorophenylsulfonyl)]phenoxy-1,3,5-triazine In a manner similar to that employed in Part B of Example XXII, cyanuric chloride was reacted with 4-chlorophenyl 4'-hydroxyphenyl sulfone prepared in Part A above in the presence of 2,6-lutidine as an acid acceptor to give 2,4-dichloro-6-[4-(4-chlorophenylsulfonyl)]phenoxy-1,3,5-triazine having a melting point of 167ºc. Elemental analysis of the product indicated the following:
Analysis: C15H8Cl3N3O3S
Calculated: C, 43.24; H, 1.93; N, 10.08
Found: C, 43.16; H, 2.01; N, 10.01
This compound is referred to hereinafter as Compound
189.
Example CXIV
Preparation of bis[4-(4,6-dichloro-1,3,5-triazine-2- yloxy)phenyl] sulfone
In a manner similar to that employed in
Part B of Example XXII, cyanuric chloride was reacted with bis(4-hydroxyphenyl) sulfone in the presence of 2,6-lutidine as an acid acceptor to give bis [4-(4,6-dichloro-1,3,5-triazin-2-yloxy)phenyl] sulfone having a melting point of 230°-235ºC.
Elemental analysis of the product indicated the following:
Analysis: C18H8Cl4N6O4
Calculated: C, 39.58; H, 1.48; N, 15.39
Found: C, 41.30; H, 1.73; N, 14.61
This compound is referred to hereinafter as Compound
190. Example CXV
Preparation of (4,6-dichloro-1,3,5-triazin-2-yl)
(4,6-dimethyoxy-1,3,5--triazin-2-yl)ether
Part A. Preparation of 2,4,6-trimethoxy¬
1,3,5-triazine
To a stirred solution of 12.0 grams (0.30 mole) of sodium hydroxide in 100 milliliters of methanol was slowly added over a one hour period 18.5 grams (0.10 mole) of cyanuric chloride in small portions while maintaining the reaction temperature at 25°C-30°C. After this period, the reaction mixture was stirred at room temperature for a two hour period. The mixture was filtered and methanol evaporated from the filtrate under reduced pressure. The residue was vacuum dried and crystallized from water to give 4.3 grams (0.025 mole) of 2,4,6-trimethoxy-1,3,5-triazine having a melting point of 122°C-129°C. Reverse phase high pressure liquid chromatographic analysis indicated the product to be of approximately 75% purity.
Part B. Preparation of sodium 4,6-dimethoxy- 1,3,5-triazin-2-olate
To a stirred solution of 1.86 grams (0.05 mole) of sodium hydroxide in 25 milliliters of methanol was added 4.0 grams (0.02 mole) of 2,4,6-tri-methoxy-1,3,5-triazine prepared in Part A above which was heated under reflux for a period of one hour. The solution was allowed to cool and the white solid collected and dried to give 3.95 grams (0.02 mole) of sodium 4,6-dimethoxy-1.3,5-triazin- 2-olate.
Part C. Preparation of (4,6-dichloro-1,3,5- triazin-2-yl) (4,6-dimethoxy-1,3,5-triazin- 2-yl) ether
Sodium 4,6-dimethoxy-1,3,5-triazin-2-olate (1.5 grams. 0.01 mole) prepared in Part B above was suspended in 25 milliliters of acetonitrile and the mixture cooled to a temperature of 5°C-10°C in an ice bath. A solution of 1.54 grams (0.01 mole) of cyanuric chloride in 25 milliliters of acetonitrile was then added dropwise with stirring while maintaining the temperature below 10ºC. The reaction mixture was stirred in the ice bath and allowed to warm slowly to room temperature. After stirring for a 16 hour period, the reaction mixture was filtered and solvent removed by evaporation. A white solid residue was purified by flash chromatography (30% ethyl acetate in hexane) to give 1.34 grams (0.004 mole) of (4,6-dichloro-1,3,5-triazin-2-yl) (4,6-dimethoxy-1,3,5-triazin-2-yl) ether having a melting point of 158.5ºC-160°C. Elemental analysis of the product indicated the following:
Analysis: C8H6Cl2N6O3
Calculated: C, 31.50; H, 1.98; N, 27.55 Found: C, 31.74; H, 2.07; N, 27.47 This compound is referred to hereinafter as Compound 191. Example CXVI Preparation of 2,2'-thiobis(4,6-dichloro- 1,3,5-triazine) To a stirred solution of 10.0 grams (0.05 mole) of cyanuric chloride in 100 milliliters of acetone was added a solution of 3.26 grams (0.01 mole) of sodium sulfide nonahydrate in 30 milliliters of water over a period of 30 minutes while maintaining the temperature of the reaction mixture at 0-5ºC by external cooling. The reaction mixture was stirred at a temperature of 0-5°C for a period of 15 minutes and 150 milliliters of ice water was added. A white precipitate formed and was immediately filtered off and dried. Unreacted cyanuric chloride was removed from the crude product by vacuum sublimation and the remaining solid recrystallized from hexane/methylene chloride to give 2,2'-thiobis(4,6-dichloro-1,3,5- triazine) as a white solid having a melting point of 140°C-145ºC. High pressure liquid chromatographic analysis showed the product to have a purity of 75%. Infrared analysis of the product indicated the following: IR (CHCl3) 1500, 1240, 850, cm-1. Mass spectrometric analysis indicated m/e 330 (calculated molecular weight 329.98). This compound is referred to hereinafter as Compound 192. Example CXVII
Preparation of (4-chloro-6-methoxy-1,3,5-triazin- 2-yl) (4.6-dimethoxy-1,3,5-triazin-2-yl) ether
Part A. Preparation of 2,4-dichloro-6-methoxy- 1,3,5-triazine
A mixture of 20.2 grams (0.11 mole) of cyanuric chloride. 18.4 grams (0.22 mole) of sodium bicarbonate, 100 milliliters of methanol and 125 milliliters of water was stirred for a period of 40 minutes at room temperature and then diluted with 100 milliliters of water and the resulting solid filtered off. The white solid was vacuum dried to give 13.4 grams (0.08 mole) of 2,4-dichloro-6-methoxy-1,3,5-triazine having a melting point of 88ºC-90°C.
Part B. Preparation of (4-chloro-6-methoxy-1,3,5- triazin-2-yl) (4,6-di-methoxy-1,3,5- triazin-2-yl) ether
To a stirred suspension of 2.91 grams (0.02 mole) of sodium 4.6-dimethoxy-1.3.5-triazin-2-olate prepared in Part B of Example CXV in 50 milliliters of acetonitrile was added dropwise a solution of 2.93 grams (0.02 mole) of 2,4-dichloro-6-methoxy-1,3,5-triazine prepared in Part-A above. The reaction mixture was heated under reflux for a period of 48 hours and then refluxed for a second 48 hour period after addition of 1.17 grams (0.003 mole) of dibenzo-18-crown-6. The mixture was allowed to cool, diluted with 75 milliliters of methylene chloride and then filtered. Af te evaporation of solvents the residue was purified by flash chromatography (20% ethyl acetate in hexane eluant) to yield 1.60 grams (0.005 mole) of (4-chloro-6-methoxy-1,3,5-triazin-2-yl) (4,6-dimethoxy-1,3,5-triazin-2-yl) ether having a melting point of 126.5°C-128°C. Elemental analysis of the product indicated the following: Analysis: C9H9ClN6O4
Calculated: C, 35.95; H, 3.01; N, 27.95 Found: C, 35.92; H, 3.12; N, 28.08 This compound is referred to hereinafter as Compound 193.
Example CXVIII Preparation of 2-chloro-4.6-dimethoxy-1,3,5-triazine A mixture of 18.5 grams (0.10 mole) of cyanuric chloride, 16.8 grams (0.20 mole) of sodium bicarbonate, 57 milliliters of methanol and 5 milliliters of water was stirred vigorously and carbon dioxide evolution was observed as the reaction temperature rose to about 40°C. After a period of 20 minutes, carbon dioxide evolution had slowed and the reaction mixture was then heated under reflux for a period of 30 minutes. The mixture was cooled and diluted with water causing a white precipitate to separate. The solid was collected, waterwashed, vacuum dried and the crude product crystallized from cyclohexane to give 10.0 grams (0.06 mole) of 2-chloro-4,6-dimethoxy-1,3,5-triazine as a white crystalline solid having a melting point of 69ºC-71ºC. Elemental analysis of the product indicated the following: Analysis: C5H6ClN3O2
Calculated: C, 34.20; H, 3.44; N, 23.93 Found: C, 34.14; H, 3.60; N, 23.96
This compound is referred to hereinafter as Compound
194.
Example CXIX
Preparation of 6-(2,4-dichlorophenylazo)- 2,4-dichloto-1,3,5-triazine
A slow stream of chlorine gas was passed for a period of ten minutes through a two-phase mixture consisting of a solution of 2.6 grams (0.008 mole) of N-(2,4-dichlorophenyl)-N'-(4,6-dichloro-1,3,5-triazin-2-yl)hydrazine in 75 milliliters of CHCl3 and a solution of 1.34 grams (0.02 mole) of NaHCO3 in 40 milliliters of water. Nitrogen was then bubbled through the mixture to remove excess chlorine and the organic layer was separated, washed with water and dried over anhydrous MgSO4 to yield 2.4 grams of a dark red solid. This was combined with 980 milligrams of product prepared from a previous identical reaction except that 1.0 gram (0.003 mole) of N-(2,4-dichlorophenyl)-N-(4,6-dichloro-1,3,5-triazin-2-yl)hydrazine was used. The combined products were flash-chromatographed on silica gel using a 9:1 v/v hexane-ethyl acetate eluent to yield the crude product as a red solid. This crude product was recrystallized from hexane to give a material which was sublimed giving 0.91 grams (0.003 mole) of 6-(2,4-dichlorophenylazo)-2,4-dichloro-1,3,5-triazine as a red solid having a melting point of 119ºC-123°C. Elemental analysis of the product indicated the following:
Analysis: C9H3Cl4N5
Calculated: C, 33.47; H, 0.94; N, 21.68
Found: C, 32.95; H, 0.97; N, 21.14
This compound is referred to hereinafter as Compound
195.
Example CXX
Preparation of 2-(4-methoxyphenyl)-4,6-dichloro- 1,3,5-triazine
In a manner similar to that employed in
Example XL, cyanuric chloride was reacted with the
Grignard reagent of 4-bromoanisole to give
2-(4-methoxy-phenyl)-4,6-dichloro-1,3,5-triazine having a melting point of 136.5°C-138.5ºC.
Elemental analysis of the product indicated the following:
Analysis: C10H7Cl2N3O
Calculated: C, 46.90; H, 2.76; N, 16.41 Found: C, 46.76; H, 2.78; N, 16.29
This compound is referred to hereinafter as Compound
196.
Example CXXI In a manner similar to that employed in Example CXX, other compounds were prepared . The structures and analytical data for Compounds 197 through 199, which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table P below.
Figure imgf000466_0001
Example CXXII Preparation of 2-[(2-phenoxy)ethoxy]-4,6- dichloro-1,3,5-triazine In a manner similar to. that employed in Example XXXII, 2-phenoxyethanol was reacted with cyanuric chloride in the presence of 2,6-lutidine as an acid acceptor to give 2-[(2-phenoxy)ethoxy]-4,6-dichloro-1,3,5-triazine having a melting point of 81°C-83°C. Elemental analysis of the product indicated the following:
Analysis: C11H9Cl2N3O2
Calculated: C, 46.17; H, 3.17; N, 14.69
Found: C, 46.41; H, 3.44: N, 14.68 This compound is referred to hereinafter as Compound 200.
Example CXXIII
Preparation of 2-[2-(2,4-dichlorophenoxy) ethoxy]-4,6-dichloro-1,3,5-triazine
Part A. Preparation of 2-(2,4-dichlorophenoxy)- ethanol
To a solution of 2.44 grams (0.06 mole) of NaOH in 20 milliliters of water was added 10.0 grams (0.06 mole) of 2,4-dichlorophenol portionwise. A 4.8 milliliter (0.07 mole) portion of 2-bromoethanol was then added and the mixture heated at a temperature of 60°C for a period of approximately
16 hours. After cooling, the reaction mixture was extracted with dichloromethane and the combined organic extracts then washed with 1N NaOH solution and water and then dried over MgSO4. Concentra tion under reduced pressure gave 8.02 grams (0.04 mole) of 2-(2,4-dichlorophenoxy)ethanol. NMR analysis of the phenol intermediate indicated the following: 'H NHR (CDCl3):δ 2.73 (m, H), 3.7-4.4 (m, 4H), 6.97 (d, H, J = 8Hz), 7.33 (dd, H, J = 3, 8 Hz), 7.47 (d, H, J = 3 Hz) ppm.
Part B. Preparation of 2-[2-(2,4-dichlorophenoxy)- ethoxy]-4,6-dichloro-1,3,5-triazine
In a manner similar to that employed in
Example XXXII, cyanuric chloride was reacted with
2-(2,4-dichlorophenoxy)ethanol prepared in Part A above in the presence of 2,6-lutidine as an acid acceptor to give 2-[2-(2,4-dichlorophenoxy)ethoxy]- 4,6-dichloro-1,3,5-triazine having a melting point of 103°C-104.5°C. Elemental analysis of the product indicated the following:
Analysis: C11H7Cl4N3O2
Calculated: C, 37.21; H, 1.99; N, 11.84 Found: C, 37.06: H, 2.19; N, 11.73
This compound is referred to hereinafter as Compound
201.
Example CXXIV
Preparation of 2-[(2,4-dichlorobenzyloxy)- ethoxyl-4,6-dichloro-1,3,5-triazine
Part A. Preparation of 2-(2,4-dichlorobenzyloxy)- ethanol
To a slurry of 125 grams of neutral alumina in 125 milliliters of ether was added 5.0 grams (0.03 mole) of 2, 4-dichlorobenzyl alcohol and 62.5 milliliters (0.12 mole) of a 2M solution of ethylene oxide in ether. This mixture was stirred for a period of approximately 16 hours at room temperature, poured into 500 milliliters of methanol and allowed to stand for 6 hours. The alumina was filtered off, washed with methanol and the filtrate concentrated under reduced pressure to give 9.26 grams of crude product as a clear liquid. This was combined with 2.6 grams of crude product prepared from a previous identical reaction except that 2.0 grams (0.01 mole) of 2,4-dichlorobenzyl alcohol was used. The combined products were flash-chromatographed using hexane-ethyl acetate (1:1 v/v) as the eluant to give 1.3 grams (0.006 mole) of 2-(2,4-dichlorobenzyloxy) ethanol as a colorless liquid. NMR analysis of this intermediate indicated the following: 'H NMR (CDCl3) : δ 2.47 (br s, H), 3.5-4.0 (m. 4H), 4.60 (s. 2H), 7.1-7.6 (m, 3H) ppm.
Part B. Preparation of 2-[(2,4-dichlorobenzyloxy)- ethoxy]-4.6-dichloro-1,3,5-triazine In a manner similar to that employed in Example XXXII, cyanuric chloride was reacted with 2-(2,4-dichlorobenzyloxy)ethanol prepared in Part A above in the presence of 2.6-lutidine as an acid acceptor to give 2-[(2,4-dichlorobenzyloxy)-ethoxy]-4,6-dichloro-1,3,5-triazine as a colorless oil. Elemental analysis of the product indicated the following: Analysis: C12H9Cl4N3O2
Calculated: C, 39.05; H, 2.46; N, 11.39
Found: C, 39.82; H, 2.55; N, 11.32
This compound is referred to hereinafter as Compound
202.
Example CXXV
Preparation of 2-(2-[2-(2,4-dichlorophenoxy)- ethoxy]ethoxy)-4,6-dichloro-1,3,5-triazine
Part A. Preparation of 2-[2-(2,4-dichlorophenoxy)- ethoxy]ethanol
In a manner similar to that employed in Part A of Example CXXIII, 2,4-dichlorophenol was reacted with 2-(2-chloroethoxy)ethanol in the presence of sodium hydroxide as an acid acceptor to give 2-[2-(2,4-dichlorophenoxy)ethoxy]ethanol as a colorless liquid. NMR analysis of this intermediate indicated the following: 'H NMR (CDCl3)δ 2.83 (br s, H)s 3.5-4.0 (m, 6H), 4.1-4.4 (m, 2H), 6.83
(d, H, J = 2 Hz), 7.20 (dd, H, J - 2.8 Hz), 7.37 (d, H, J = 2 Hz) ppm.
Part B. Preparation of 2-(2-[2-(2,4-dichlorophenoxy)ethoxy]ethoxy)-4,6-dichloro- 1,3,5-triazine
In a manner similar to that employed in Example XXXII, cyanuric chloride was reacted with 2-[2-(2,4-dichlorophenoxy)ethoxy]ethanol prepared in Part A above in the presence of 2,6-lutidine as an acid acceptor to give 2-(2-[2-(2,4-dichlorophenoxy)- ethoxy]ethoxy)-4,6-dichloro-1,3,5-triazine. having a melting point of 59.5°C-61.5ºC. Elemental analysis of the product indicated the following:
Analysis: C13H11Cl4N3O3
Calculated: C, 39.12; H, 2.78; N, 10.53
Found: C, 38.65; H, 2.76; N, 10.71
This compound is referred to hereinafter as Compound
203.
Example CXXVI
Preparation of 2-[4-(2,4-dichlorophenyl)butoxy]- 4.6-dichloro-1,3,5-triazine
Part A. Preparation of 2-(2,4-dichlorophenyl) ethyl bromide
A mixture of 30.1 grams (0.16 mole) of 2,4-dichlorophenethyl alcohol prepared in Part A of Example XLVIII and 140 milliliters of 48% aqueous HBr was heated under reflux for a period of 5 hours. After cooling, the reaction mixture was partioned between ether and water and the ethereal phase then extracted with saturated aqueous NaHCO3, dried over MgSO4 and concentrated under reduced pressure to give a brown liquid. Kugelrohr distillation gave 29.7 grams (0.12 mole) of 2-(2,4-dichloro- phenyl)ethyl bromide as a colorless liquid having a boiling point of 70°C at 0.025 mm Hg. NMR analysis of this intermediate indicated the following: 'H NMR (CDCl3) δ 3.0-3.8 (m, 4H), 7.0-7.4 (m, 3H) ppm. Part B. Preparation of 4-(2,4-dichlorophenyl)- butan-1-ol
To 0.96 grams (0.04 mole) of magnesium turnings in 20 milliliters of anhydrous tetrahydrofuran was added dropwise a solution of 2-(2,4-dichloro-phenyl)ethyl bromide prepared in Part A above in 30 milliliters of tetrahydrofuran. When the magnesium had been consumed, the yellow solution of Grignard reagent was added dropwise to a cold (-30°C) mixture of 1.9 grams (0.01 mole) of curpous iodide in 30 milliliters of tetrahydrofuran. This mixture was stirred for a period of 5 minutes and 35 milliliters of tetrahydrofuran was added. This mixture was stirred for a period of 5 minutes and 35 milliliters (0.07 mole) of a 2M solution of ethylene oxide was then added dropwise. The reaction mixture was stirred for a period of 2 hours at a temperature of 0°C and a 1 hour period at room temperature and then quenched with 50 milliliters of water. The volume was reduced in vacuo and the residue extracted with ether. The ethereal layer was dried (MgSO4) and concentrated under reduced pressure to give a liquid which was chromatographed on silica gel to give 2.37 grams (0.01 mole) of 4-(2,4-dichlorophenyl)butan-1-ol as a pale yellow liquid. NMR analysis of this intermediate indicated the following: 'H NMR (CDCl3)δ 1.43-1.83 (m, 4H), 2.53-2.90 (m, 3H), 3.50-3.77 (m, 2H), 7.07 (m, 2H), 7.33 (m, H) ppm. Part C. Preparation of 2-[4-(2,4-dichlorophenyl)- butoxyl-4,6-dichloro-1,3,5-triazine
In a manner similar to that employed in
Example XXXII, cyanuric chloride was reacted with
4-(2,4-dichlorophenyl)butan-1-ol prepared in Part B above in the presence of 2,6-lutidine as an acid acceptor to give 2-[4-(2,4-dichlorophenyl)butoxy]-
4,6-dichloro-1,3,5-triazine as a pale yellow oil.
Elemental analysis of the product indicated the following:
Analysis: C13H11Cl4N3O
Calculated: C, 42.53; H, 3.02; N, 11.45
Found: C, 43.30; H, 3.08; N, 10.76
This compound is referred to hereinafter as Compound
204.
Example CXXVII Preparation of 2,4-dichloro-6-(2,4-dichloro- 3,5-dimethylphenoxy)-1,3,5-triazine In a manner similar to that employed in Example I, cyanuric chloride was reacted with 2,4-dichloro-3,5-dimethylphenol in the presence of 2,6-lutidine as an acid acceptor to give 2,4-dichloro-6-(2,4-dichloro-3,5-dimethylphenoxy)-1,3,5-triazine having a melting point of 118ºC-120ºC. Elemental analysis of the product indicated the following:
Analysis: C11H7Cl4N3O
Calculated: C, 38.97; H, 2.08; N, 12.39
Found: C, 39.18; H, 2.25; N, 12.47 This compound is referred to hereinafter as Compound 205.
Example CXXVIII In a manner similar to that employed in Example CXXVII, other compounds were prepared. The structures and analytical data for Compounds 206 through 210, which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table Q below.
Figure imgf000475_0001
Example CXXIX
Preparation of acetone O-(4,6-dichloro-1,3,5- triazin-2-yl)oxime
In a manner similar to that employed in
Example XXXVI, cyanuric chloride was reacted with acetone oxime in the presence of sodium bicarbonate as an acid acceptor to give acetone O-(4,6-dichloro- 1,3,5-triazin-2-yl)oxime having a melting point of
60ºC-62°C. Elemental analysis of the product indicated the following:
Analysis: C6H6CI2N4O Calculated: C, 32.60; H, 2.74; N, 25.35
Found: C, 32.24; H, 2.90; N, 25.28
This compound is referred to hereinafter as Compound
211.
Example CXXX In a manner similar to that employed in Example LXXIII, other compounds were prepared. The structures and analytical data for Compounds 212 and 213. which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table R below.
Figure imgf000477_0001
Example CXXXI
Preparation of 2-chloro-4-ethynyl-6-methoxy- 1,3,5-triazine
To 1.0 gram (0.004 mole) of
2,4-dichloro-6-trimethylsilylethynyl-1,3,5-triazine prepared in Example LXXII in methanol solution was added 0.235 gram (0.004 mole) of potassium fluoride at at temperature of 0°C. The reaction mixture was stirred for a period of 30 minutes, a saturated aqueous solution of ammonium chloride was added and the methanol then evaporated in vacuo. The residue was extracted with ether and the ether solution was dried over Na2SO4, filtered and evaporated to give 0.33 gram (0.002 mole) of 2-chloro-4-ethynyl-6-methoxy-1,3,5-triazine having a melting point of 108°C-110ºC. Elemental analysis of the product indicated the following:
Analysis: C6H4ClN3O
Calculated: C, 42.50; H, 2.38; N, 24.78 Found: C, 41.58; H, 2.29; N, 23.91 This compound is referred to hereinafter as Compound 214.
Example CXXXII In a manner similar to that employed in Example LXI, other compounds were prepared. The structures and analytical data for Compounds 215 through 217, which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table S below.
Figure imgf000479_0001
Example CXXXIII
Preparation of 2,4-dichloro-6-phenylsulfonamido- 1,3,5-triazine
In a manner similar to that employed in
Example LXXIV, cyanuric chloride was reacted with benzenesulfonamide in the presence of sodium hydroxide as an acid acceptor to give 2,4-dichloro-6-phenylsulfonamido-1,3,5-triazine having a melting point of 185°C-186°C. Elemental analysis of the product indicated the following:
Analysis: C9H6Cl2N4O2S Calculated: C, 35.42; H, 1.98; N, 18.36
Found: C; 35.04; H, 2.32; N, 18.09
This compound is referred to hereinafter as Compound
218.
Example CXXXIV Preparation of 2-chloro-4-(2,4-dichlorophenoxy)- 6-hexafluoroisopropoxy-1,3,5-triazine To a solution of 5.0 grams (0.02 mole) of 2,4-dichloro-6-(2,4-dichlorophenoxy)-1,3,5-triazine prepared in Example IV in 100 milliliters of acetone was added at a temperature of 40°C a solution of 1.9 milliliters (0.02 mole) of 2,6-lutidine in 75 milliliters of acetone followed by a solution of 1.9 milliliters (0.02 mole) of hexafluoroisopropyl alcohol in 75 milliliters of acetone. The resulting mixture was heated under reflux for a period of 10 hours and then evaporated to dryness in vacuo. The residue was subjected to flash column chromatography on silica gel by first eluting with 5% ethyl acetate in hexane and then with 15% dichloromethane in hexane to give 1.34 grams (0.0035 mole) of 2-chloro-4-(2,4-dichlorophenoxy)-6-hexafluoroisopropoxy-1,3,5-triazine as an oil. Elemental analysis of the product indicated the following:
Analysis: C12H4Cl3F6N3O2
Calculated: C, 37.38; H, 1.05; N, 10.90
Found: C, 32.52; H, 0.89; N, 9.48
This compound is referred to hereinafter as Compound
219.
Example CXXXV
Preparation of 2-chloro-4-(1-naphthoxy)-6- (2,2,2-trifluoroethoxy)-1,3,5-triazine
In a manner similar to that employed in Example CXXXIV, 2,4-dichloro-6-(1-naphthoxy)-1,3,5-triazine prepared in Example IX was reacted with 2,2,2-trifluoroethanol in the presence of 2,6-lutidine as an acid acceptor to give 2-chloro-4-(1-naphthoxy)-6-(2,2,2-trifluoroethoxy)-1,3,5-triazine as an oil. Elemental analysis of the product indicated the following:
Analysis: C15H19ClFN3O
Calculated: C, 50.65; H, 2.55; N, 11.81
Found: C, 51.04; H, 2.75; N, 11.53
This compound is referred to hereinafter as Compound
220. Example CXXXVI Preparation of 2-chloro-4-(2,4-dichlorophenoxy)- 6-ethoxy-1,3,5-triazine To a suspension of 0.39 gram (0.02 mole) of magnesium in 70 milliliters of dry tetrahydrofuran was added a solution of 3.17 grams (0.02 mole) of bromoacetaldehyde diethyl acetal in 10 milliliters of dry tetrahydrofuran. The resulting mixture was stirred at room temperature for a period of 1 hour and a solution of 5.0 grams (0.02 mole) of 2,4-dichloro-6-(2,4-dichloro-phenoxy)-1,3,5-triazine was then added dropwise. The reaction mixture was stirred at room temperature for a period of approximately 16 hours, evaporated to dryness and the residue purified by flash-column chromatography on silica gel by eluting with 5% ethyl acetate in hexane to give 1.9 grams (0.01 mole) of 2-chloro-4-(2,4-dichlorophenoxy)-6-ethoxy-1,3,5-triazine as an oil. Elemental analysis of the product indicated the following:
Analysis: C11H8Cl3N3O2
Calculated: C, 41.22; H.-2.51; N, 13.11
Found: C, 41.24; H, 2.50; N, 12.75
This compound is referred to hereinafter as Compound
221.
Example CXXXVII Preparation of 2,4-dichloro-6-(2,2,2- trichloroethoxy)-1,3,5-triazine To a solution of 5.0 grams (0.03 mole) of cyanuric chloride in 100 milliliters of acetone was added at a temperature of 4°C a solution of 3.16 milliliters (0.03 mole) of 2,6-lutidine followed by a solution of 2.60 milliliters (0.03 mole) of 2,2,2-trichloroethanol in 150 milliliters of acetone. The mixture was stirred at room temperature for a period of about 16 hours and the solvent was removed by evaporation. The residue was partitioned between water and dichloromethane, the organic layer dried over anhydrous sodium sulfate and the residue, following evaporation of solvents, purified by flash column chromatography on silica gel. Elution by ethyl acetate-hexane gave 1.1 grams
(0.004 mole) of 2,4-dichloro-6-(2,2,2-trichloroethoxy)-1,3,5-triazine as yellow crystals having a melting point of 72°C-73°C. Elemental analysis of the product indicated the following: Analysis: C5H2Cl5N3O Calculated: C, 20.20; H, 0.68; N, 14.13 Found: C, 20.19; H, 0.68; N, 14.48 This compound is referred to hereinafter as Compound 222.
Example CXXXVII I Preparation of 2,4-dichloro-6-[2-(N- methylpyrrolyl)]-1,3,5-triazine A mixture of 2.4 milliliters (0.03 mole) of N-methylpyrrole, 5.0 grams (0.03 mole) of cyanuric chloride and 50 milliliters of p-dioxane was heated under reflux for a period of 5 hours. The reaction mixture was poured into water and the precipitate which formed was collected by suction filtration and dried. Crystallization from hexane gave 2.0 grams (0.01 mole) of 2,4-dichloro-6-[2-(N-methylpyrrolyl)]-1,3,5-triazine as pale yellow crystals having a melting point of 153ºC-154ºC. Elemental analysis of the product indicated the following:
Analysis: C8H6Cl2N4
Calculated: C, 41.95; H, 2.64; N, 24.46
Found: C, 42.00; H, 2.73: N, 24.46
This compound is referred to hereinafter as Compound
223.
Example CXXXIX Preparation of N-(4,6-dichloro-1,3.5-triazin-2- yl)-2-oxohexamethyleneimine To a suspension of 10.0 grams (0.09 mole) of potassium hydride in oil was added 200 milliliters of dry tetrahydrofuran at a temperature of -60°C followed by the addition of 10.0 grams (0.09 mole) of ε- caprolactam at the same temperature. The mixture was warmed to room temperature and stirred for a period of one hour after which a solution of 16.3 grams (0.09 mole) of cyanuric chloride in 100 milliliters of tetrahydrofuran was added and stirring continued for an additional two hour period. The reaction mixture was vacuum evaporated and the residue purified by flash chromatography to give 1.2 grams (0.005 mole) of N-(4,6-dichloro-1,3,5-triazin-2-yl)-2-oxohexamethyleneimine as an oil. Elemental analysis of the product indicated the following: Analysis: C9H10Cl2N4O
Calculated: C, 41.40; H, 3.86; N, 21.46
Found: C, 40.85; H, 4.40; N, 21.01
This compound is referred to hereinafter as Compound
224.
Example CXL Preparation of N-(4,6-dichloro-1,3,5-triazin- 2-yl)-2-oxotetramethyleneimine In a manner similar to that employed in Example CXXXIX, 2-pyrrolidinone was treated with potassium hydride and the resulting potassium salt was then reacted with cyanuric chloride to give N-(4,6-dichloro-1,3,5-triazin-2-yl)-2-oxotetramethyleneimine having a melting point of 192ºC-194°C. Elemental analysis of the product indicated the following:
Analysis: C7H6Cl2N4O
Calculated: C, 36.07; H, 2.60; N, 24.04
Found: C, 35.86; H, 2.54: N, 24.01
This compound is referred to hereinafter as Compound
225.
Example CXLI Preparation of N-(4,6-dichloro-1,3,5-triazin- 2-yl)-1,3,3-trimethyl-6-aza-bicyclo [3.2.1]octane and 2,4-bis(1,3,3-trimethyl-6-azabicyclo [3.2.1] octan-6-yl)-6-chloro-1,3,5-triazine In a manner similar to that employed in Example CXXXIX, 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane was treated with potassium hydride and the resulting potassium salt was then reacted with cyanuric chloride to give N-(4, 6-dichloro-l, 3,5- triazin-2-yl)-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane having a melting point of 133ºC-135°C and 2,4-bis (1,3,3-trimethyl-6-azabicyclo [3.2.1] octan-6-yl)-6-chloro-1,3,5-triazine having a melting point of 161.5ºC-163ºC by separating the two products by flash column chromatography. Elemental and NMR analysis of the two products indicated the following:
N-(4,6-dichloro-1,3,5-triazin-2-yl)-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane
Analysis: C12H18Cl2N3
Calculated: C, 51.83; H, 6.02; N, 18.60;
Cl, 23.54 Found: C, 51.82; H, 5.81; N, 18.47; Cl, 23.78 This compound is referred to hereinafter as Compound 226. 2,4-Bis(1,3,3-trimethyl-6-azabicyclo[3.2.1]octan- 6-yl)-6-chloro-1,3,5-triazine
'H NMR (CDCl3):δ 0.80 (s, 6H), 0.94 (s, 6H). 1.10 (s, 6H), 1.30-2.30 (m, 12H), 2.90-3.70 (m. 4H), 4.30-4.68 (m, 2H) ppm.
This compound is referred to hereinafter as Compound 227.
Example CXLII
Preparation of 4,6-dichloro-2-(3-phenylphenoxy)- 1,3,5-triazine
In a manner similar to that employed in Example X, cyanuric chloride was reacted with 3-phenylphenol in the presence of triisopropanolamine as an acid acceptor to give 4,6-dichloro-2-(3-phenylphenoxy)-1,3,5-triazine having a melting point of 183ºC-185°C. Elemental analysis of the product indicated the following:
Analysis: C15H9N3O
Calculated: C, 56.63; H, 2.85; N, 13.21;
Cl, 22.29 Found: C, 56.33; H, 3.29; N, 13.15; Cl, 21.55 This compound is referred to hereinafter as Compound 228. Example CXLIII
Preparation of 2,3-dichloro-N-(2-chloroanilino) maleimide
A stirred mixture of 5.0 grams (0.03 mole) of o-chlorophenylhydrazine hydrochloride. 4.7 grams
(0.03 mole) of dichloromaleic anhydride and 20 milliliters of acetic acid was heated at a temperature of 100°C for a period of 45 minutes.
The mixture was cooled to room temperature and water was added dropwise causing a precipitate to form.
The first crop of product was filtered off and a second crop was obtained by slow evaporation of the mother liquor and a second filtration. Combining the two crops gave 5.55 grams (0.02 mole) of
2,3-dichloro-N-(2-chloroanilino)maleimide as yellow crystals having a melting point of 137°C-138°C.
Elemental analysis of the product indicated the following:
Analysis: C10H5Cl3N2O2
Calculated: C, 41.20; H, 1.73; N, 9.61 Found: C, 40.80; H, 1.97; N, 9.75
This compound is referred to hereinafter as Compound
229.
Example CXLIV In a manner similar to that employed in Example CXLIII, other compounds were prepared. The structures and analytical data for Compounds 230 through 250. which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table T below.
Figure imgf000489_0001
Figure imgf000490_0001
Figure imgf000491_0001
Figure imgf000492_0001
Figure imgf000493_0001
Figure imgf000494_0001
Figure imgf000495_0001
Example CXLV Preparation of 6-hydroχy-2-phenyl- 3(2H)pyridazinone A stirred mixture of 10 milliliters (0.10 mole) of phenylhydrazine. 10 grams (0.10 mole) of maleic anhydride and 75 milliliters of acetic acid was heated under reflux for a period of 6 hours. The mixture was cooled to room temperature causing separation of crystals which were filtered off giving 10.62 grams (0.05 mole) of 6-hydroxy-2-phenyl-3(2H)pyridazinone as yellow crystals having a melting point of 262°C (decomposition). NMR analysis indicated the following: 'H NMR (CDCl3):δ 7.21 (ABq, 2H, J = 10 Hz), 7.50-7.87 (m, 5H) ppm.
This compound is referred to hereinafter as Compound 251.
Example CXLVI Preparation of 4,6-dichloro-2-phenyl- 3(2H)pyridazinone A stirred mixture of 30 milliliters (0.32 mole) of phosphorus oxychloride. 30 grams (0.14 mole) of phosphorus pentachloride and 5.0 grams (0.024 mole) of 6-hydroxy-2-phenyl-3(2H)pyridazinone prepared in Example CXLV was heated at a temperature of 160ºC-170ºC for a period of 90 minutes. The mixture was cooled to room temperature and poured into ice water giving a yellow precipitate. The crude product was filtered off and crystallized from methylene chloride-hexane to give 2.1 grams (0.01 mole) of 4,6-dichloro-2-phenyl-3(2H)pyridazinone as yellow crystals having a melting point of 110ºC-111ºC. Elemental analysis of the product indicated the following: Analysis: C10H6Cl2N2O Calculated: C, 49.33; H, 2.56; N, 11.18 Found: C, 49.69; H, 2.61; N, 11.57 This compound is referred to hereinafter as Compound 252.
Example CXLVII Preparation of 6-chloro-2-phenyl-3(2H)pyridazinone
A stirred mixture of 2.0 grams (0.01 mole) of 6-hydroxy-2-phenyl-3-(2H)pyridazinone prepared in Example CXLV and 20 milliliters (0.21 mole) of phosphorus oxychloride was heated at a temperature of 95°C for a period of 2 hours. The reaction mixture was cooled to room temperature and then quenched with ice water. Hexane was added and the mixture was triturated giving white crystals. These crystals were filtered off to give 0.81 gram (0.004 mole) of 6-chloro-2-phenyl-3(2H)pyridazinone as off-white crystals having a melting point of 112°C-113°C. Elemental analysis of the product indicated the following:
Analysis: C10H7ClN2O
Calculated: C, 58.13; H, 3.42; N, 13.56; Cl. 17.16
Found: C, 58.10; H, 3.10; N, 13.41: Cl. 16.47 This compound is referred to hereinafter as Compound 253.
Example CXLVIII Preparation of 4,5-dichloro-6-hydroχy-2- (2,4-dichlorophenyl)-3(2H)pyridazi-none Into a mixture of 18.8 grams (0.09 mole) of 2,4-dichlorophenylhydrazine hydrochloride and 600 milliliters of 6N hydrochloric acid was added 14.7 grams (0.09 mole) of dichloromaleic anhydride. The mixture was heated under reflux for a period of 6 hours and the resulting solid was filtered off and washed with ice water and hexane to give 7.6 grams (0.023 mole) of 4,5-dichloro-6-hydroxy-2-(2,4-dichlorophenyl)-3(2H)pyridazinone having a melting point of 295°C-298°C (decomposition). Elemental analysis of the product indicated the following:
Analysis: C10H4Cl4N2O2
Calculated: C, 36.85; H, 1.24; N, 8.59
Found: C, 36.69; H, 1.37; N, 8.44
This compound is referred to hereinafter as Compound
254.
Example CXLIX Preparation of 4,5-dichloro-6-hydroχy-2- (2-chlorophenyl)-3(2H)pyridazinone In a manner similar to that employed in Example CXLVIII. o-chloro-phenylhydrazine hydrochloride was reacted with dichloromaleic anhydride to give 4,5-dichloro-6-hydroxy-2-(2-chlorophenyl)-3(2H)pyridazinone having a melting point of 242ºC-244ºC. Elemental analysis of the product indicated the following:
Analysis: C10H5Cl3N2O2 Calculated: C, 41.20; H, 1.73; N, 9.61 Found: C, 41.19; H, 1.97; N, 9.60 This compound is referred to hereinafter as Compound 255.
Example CL Preparation of 4,5-dichloro-6-hydroxy-2- (3,4-dichlorophenyl)-3(2H)pyridazi-none A stirred mixture of 7.5 grams (0.03 mole) of 3,4-diphenylhydrazine hydrochloride, 5.0 grams (0.3 mole) of dichloromaleic anhydride and 100 milliliters of glacial acetic acid was heated under reflux for a period of 2 days. The mixture was cooled to room temperature causing yellow-orange crystals to separate. Suction filtration of the crystals gave 2.87 grams (0.01 mole) of 4,5-dichloro-6-hydroxy-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone having a melting point of 241°C-242.5°C. Elemental analysis of the product indicated the following:
Analysis: C10H4Cl4N2O2
Calculated: C, 36.85; H, 1.24; N, 8.59
Found: C, 36.47; H, 2.07; N, 7.49
This compound is referred to hereinafter as Compound
256. Example CLI Preparation of 2,3-dichloro-N-(2-methylanilino)- maleimide and 4,5-dichloro-6-hydroxy-2- (2-methylphenyl)-3(2H)pyridazinone In a manner similar to that employed in Example CXLIII, o-tolylhydrazine hydrochloride was reacted with dichloromaleic anhydride to give 2,3-dichloro-N-(2-methylanilino)maleimide having a melting point of 146ºC-149ºC and 4,5-dichloro-6-hydroxy-2-(2-methylphenyl)-3 (2H)pyridazinone having a melting point of 234ºC-235.5ºC by separating the two products by recrystallization from methylene chloride. Elemental analysis of these two products indicated the following:
2.3-dichloro-N-(2-methylanilino)maleimide
Analysis: C11H8Cl2N2O2
Calculated: C, 48.73; H, 2.97; N, 10.33
Found: C, 48.64; H, 3.12; N, 10.23
This compound is referred to hereinafter as Compound
257.
4,5-dichloro-6-hydroxy-2-(2-methylphenyl)-3(2H)pyridazinone
Analysis: C11H8Cl2N2O2
Calculated: C, 48.73; H, 2.97; N, 10.33
Found: C, 48.29; H, 3.06; N, 10.16
This compound is referred to hereinafter as Compound
258. Example CLII Preparation of 4,5,6-trichloro-2-(2,4- dichlorophenyl)-3(2H)pyridazinone A stirred mixture of 3.7 grams (0.02 mole) of phosphorus pentachloride, 37 milliliters (0.4 mole) of phosphorus oxychloride and 7.6 grams (0.023 mole) of 4,5-dichloro-6-hydroxy-2-(2,4-dichlorophenyl)-3(2H)pyridazinone prepared in Example CXLVIII was heated at a temperature of 160ºC-170ºC for a period of 14 hours. The mixture was cooled to room temperature and poured into ice water with addition of a small amount of hexane and stirring to promote precipitation. The crude product was filtered, washed with ice water and purified by flash chromatography tm silica gel by eluting with 5% ethyl acetate in hexane to give 0.85 gram (0.0025 mole) of 4,5,6-trichloro-2-(2,4-dichlorophenyl)-3(2H)pyridazinone having a melting point of 154°C-155.5°C. Elemental analysis of the product indicated the following:
Analysis: C10H3Cl5N2O
Calculated: C, 34.88; H, 0.88; N, 8.13
Found: C, 34.30; H, 0.96; N, 8.20
This compound is referred to hereinafter as Compound
259.
Example CLIII In a manner similar to that employed in Example CLII, other compounds were prepared. The structure and analytical data for Compounds 260 through 264, which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table U below.
Figure imgf000503_0001
Example CLIV
Preparation of 2,3-dimethyl-N-(2-chloroanilino)maleimide
A stirred mixture of 7.1 grams (0.04 mole) of o-chlorophenylhydrazine hydrochloride. 5.0 grams
(0.04 mole) of 2.3-dimethylmaleic anhydride and 25 milliliters of acetic acid was heated at a temperature of 100°C for a period of 1 hour. The reaction mixture was cooled to room temperature and water was added dropwise causing a precipitate to form. The precipitate was filtered off and the filtrate was cooled causing the crude product to separate as a solid. The solid was crystallized from methylene chloride-hexane to give 2.3 grams
(0.01 mole) of 2,3-dimethyl-N-(2-chloroanilino)maleimide as orange crystals having a melting point of 115°C-117.5°C. Elemental analysis of the product indicated the following:
Analysis: C12H11ClN2O2
Calculated: C, 57.49; H, 4.42; N, 11.17 Found: C, 57.49; H, 4.32; N, 11.15
This compound is referred to hereinafter as Compound
265.
Example CLV In a manner similar to that employed in Part B of Example LXXXIII, other compounds were prepared. The structures and analytical data for Compounds 266 and 267, which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table V below.
Figure imgf000505_0001
Example CLVI Preparation of N-Hydroxymaleiraide N-Hydroxymaleimide having a melting point of 133ºC-135ºC was purchased from the Aldrich Chemical Company and used without further purification. A log P determination for the product indicated the following: Octanol/Water Log P by Reversed Phase HPLC 0.00.
This compound is referred to hereinafter as Compound 268.
Example CLVII Preparation of 4,5-dichloro-6-hydroxy-2- (3-trifluoromethylphenyl)-3(2H)pyridazinone In a manner similar to that employed in Example CXLVIII, m-trifluoro-methylphenylhydrazine hydrochloride was reacted with dichloromaleic anhydride to give 4,5-dichloro-6-hydroxy-2-(3-trifluoromethylphenyl)-3(2H)pyridazinone having a melting point of 171ºC-172ºC. Elemental analysis of the product indicated the following:
Analysis: C11H5Cl2F3N2O2 Calculated: C, 40.64; H, 1.55; N, 8.62 Found: C, 40.55; H, 1.50; N, 8.61
This compound is referred to hereinafter as Compound
269. Example CLVIII In a manner similar to that employed in Example CXLIII, other compounds were prepared. The structures and analytical data for Compounds 270 through 275, which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table W below.
Figure imgf000508_0001
Figure imgf000509_0001
Example CLIX
Preparation of 2-methyl-4,5,6-trichloro- 3(2H)pyridazinone
Part A. Preparation of 2-methyl-4,5-dichloro- 6-hvdroxy-3 (2H)pyridazinone In a manner similar to that employed in Example CXLVIII, methyl hydrazine was reacted with dichloromaleic anhydride in aqueous HCl solution to give 2-methyl-4,5-dichloro-6-hydroxy-3(2H)pyridazinone having a melting point of 229°C-230ºC.
Part B. Preparation of 2-methyl-4,5,6-trichloro- 3(2H)pyridazinone
A mixture of 3.0 grams (0.02 mole) of 2-methyl-4,5-dichloro-6-hydroxy-3(2H)pyridazinone prepared in Part A above and 20 milliliters of phosphorus oxychloride was warmed until a solution was obtained and the excess of phosphorus oxychloride was evaporated under reduced pressure. The residue was immersed in ice water and this mixture was then stirred for a period of 1 hour giving a slurry of a buff solid which was isolated and dried over P2O5 to give 0.6 gram (0.003 mole) of 2-methyl-4,5,6-trichloro-3(2H)pyridazinone having a melting point of 96°C-98°C. This compound is referred to hereinafter as Compound 276. Example CLX Preparation of 2-benzyl-4,5-dichloro- 3(2H)pyridazinone
Part A. Preparation of 4,5-dichloro- 3(2H)pyridazinone
To a refluxing solution of 33.6 grams (0.2 mole) of mucochloric acid in 160 milliliters of absolute ethanol was. slowly added a solution of 6.7 grams (0.2 mole) of 95% hydrazine in 20 milliliters of ethanol. Refluxing was continued for a period of 2 hours after completing the feed and the mixture was then cooled causing separation of solids which were filtered off and air dried to give 24.4 grams (0.15 mole) of 4,5-dichloro-3 (2H)pyridazinone having a melting point of 193ºC-194°C.
Part B. Preparation of 2-benzyl-4,5-dichloro- 3(2H)pyridazinone
A mixture of 6.6 grams (0.04 mole) of 4,5-dichloro-3(2H)pyridazinone prepared in Part A above. 9.1 milliliters (0.08 mole) of benzyl chloride, 20 grams (0.14 mole) of potassium carbonate and 120 milliliters of N,N-dimethylformamide was heated at a temperature of 40°C-90°C causing the mixture to form a gel. The mixture was acidified, extracted with ether/acetone and filtered to give a brown solid. The filtrate was partitioned between ether and water, the ether phase washed with 10% sodium carbonate solution and with water, and then dried and evaporated to give 0.5 gram (0.002 mole) of 2-benzyl-4,5-dichloro-3(2H)pyridazinone as white crystals having a melting point of 81ºC-82ºC. This compound is referred to hereinafter as Compound 277.
Example CLXI Preparation of 2-(o-chlorobenzyl)-4,5-dichloro- 3(2H)pyridazinone A mixture of 3.4 grams (0.02 mole) of mucochloric acid, 5.1 grams (0.02 mole) of o-chlorobenzylhydrazine H2SO4 salt and 50 milliliters of absolute ethanol was heated under reflux for a period of 6 hours. The mixture was cooled and the precipitate which formed was collected and air-dried to give 3.8 grams (0.01 mole) of 2-(o-chlorobenzyl)-4,5-dichloro-3(2H)-pyridazinone as white crystals having a melting point of 114ºC.
This compound is referred to hereinafter as Compound 278.
Example CLXII Preparation of 2-chloro-N-(2-methylphenyl)- maleimide
Part. A. Preparation of 2-(or 3-)chloro-N-(2-methylphenyl)maleamic acid
A mixture of 132 grams (1.0 mole) of chloromaleic anhydride and xylene was stirred and heated at a temperature of 70ºC while slowly feeding in 107 grams (1.0 mole) of 2-methylaniline by means of a dropping funnel. On completing the
2-methylaniline feed, the reaction mixture was stirred for a period of one hour at a temperature of 70ºC. The mixture was then cooled and a solid filtered off, washed with xylene. and hexane and then dried at room temperature to give 225 grams (0.94 mole) of 2-(or 3-)chloro-N-(2-methylphenyl)-maleamic acid having a melting point of 110°C.
Part B. Preparation of 2-chloro-N-(2-methylphenyl)maleimide
To a stirred mixture of 8 grams (0.10 mole) of sodium acetate and 95.0 grams (0.40 mole)
of 2-(or 3-)chloro-N-(2-methylphenyl)maleamic acid prepared in Part A above was added 122.0 grams (1.2 moles) of acetic anhydride at room temperature and the resulting mixture then stirred and heated at a temperature of 80ºC for a period of 40 minutes. The reaction mixture was then cooled to a temperature of 25°C and added to 2 liters of ice water. The resulting mixture was extracted with 600 milliliters of ethyl ether and the ether extract then distilled through a one-foot unpacked column to give 75.0 grams (0.34 mole) of 2-chloro-N-(2-methylphenyl)maleimιde having a boiling point of 132°C at 2 mm Hg.
This compound is referred to hereinafter as Compound 279. Example CLXI I I In a manner similar to that employed in Example CLXII, other compounds were prepared. The structures and analytical data for Compounds 280 through 283. which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table X below.
Figure imgf000515_0001
Example CLXIV
Preparation of N-ethylmaleliaide N-Ethylmaleimide was purchased from the Aldrich Chemical Company and used without further purification. A log P determination for the product indicated the following: Octanol/Water Log P by Reversed Phase HPLC 1.10.
This compound is referred to hereinafter as Compound 284.
Example CLXV Additional compounds were purchased from the Maybridge Chemical Company. Limited, Trevillet, Tintagel, Cornwall. United Kingdom and evaluated for activity. The structures and analytical data for Compounds 285 through 288. which compounds are used in the examples hereinafter for reducing moisture loss from plants, are set forth in Table Y below.
Figure imgf000517_0001
Figure imgf000518_0001
Example CLXVI Preparation of 2-(3-trifluoromethyl)-4.5- dichloro-3 (2H)pyridazinone
2-(3-Trifluoromethyl)-4.5-dichloro-3(2H)pyrid azinone was purchased from the Aldrich Chemical Company and used without further purification- A log P determination for the product indicated the following: Octanol/Water Log P by Reversed Phase HPLC 2.90.
This compound is referred to hereinafter as Compound 289.
Example CLXVII Preparation of N-(2-ethoxyphenyl)succinimide
A mixture of 50 grams (0.5 mole} of succinic anhydride and 300 milliliters of toluene was stirred and heated at a temperature of 115ºC-120°C and 69 grams (0.5 mole) of 2-ethoxyaniline was fed to this mixture from a dropping funnel. The reaction mixture was then heated to boiling and toluene distilled off to a kettle temperature of l80°C-190ºC. The mixture was heated at a temperature of 180°C-190°C until the theoretical amount of water distilled from the system. The reaction mixture was cooled, diluted wiih one liter of 99% isopropyl alcohol and allowed to stand for a period of about 16 hours. The separated solid was filtered off. washed with isopropyl alcohol and dried to give 72.0 grams (0.33 mole) of N-(2-ethoxyphenyl)succinimide having a melting point of 108°C. Elemental analysis of the product indicated the following:
Analysis: C12H13NO3
Calculated: N, 6.39
Found: N, 6.73 This compound is referred to hereinafter as Compound 290.
Example CLXVIII Preparation of 3,5-dichloro-6-(3,5-dichloro- 4-methoxyphenyl)-4-hydroxypyridazine 3 ,5-dichloro-6-(3,5-dichloro-4-methoxyphenyl)-4-hydroxypyridazine was obtained as a sample from the Chemie Linz Company and used without further purification. NMR analysis of the product indicated the following: 'H NMR (CDCl3/DMSO-d6)δ 164.50, 152.77, 147.92, 141.99, 131.05, 130.58, 128.88, 128.34 and 60.51 ppm.
This compound is referred to hereinafter as Compound 291.
Example CLXIX In a manner similar to that employed in Example CXLIII, other compounds were prepared. The structures and analytical data for Compounds 292 through 296, which compounds are used in the examples hereinafter for reducing moisture loss from plants are set forth in Table Z below.
Figure imgf000521_0001
Figure imgf000522_0001
Example CLXX
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion Resistance and Transpiration Rate
Leaf diffusion resistance is a measurement of the resistance to diffusion of water vapor from a leaf and is indicative of the transpiration rate. Transpiration rate is a measurement of the evaporation of water from cell walls and diffusion of the water out of the leaf through the stomata for a given time period. The relationship between leaf diffusion resistance and transpiration rate can be summarized as follows: the higher the leaf diffusion resistance, the lower the transpiration rate; and the lower the leaf diffusion resistance, the higher the transpiration rate. As used in Table AA below, leaf diffusion resistance and transpiration rate were determined according to the following general procedure:
Solutions of the test compounds were prepared by dissolving 30.3 milligrams of compound in 5.5 milliliters of acetone and then adding water to a final volume of 11.0 milliliters. If clouding of the solution occurred as the water was added, the use of water was discontinued and acetone was added to a final volume of 11.0 milliliters. The resulting stock solutions contained 2530 parts per million by weight of compound. The test concentrations in parts of the test compound per million parts by weight of final solution employed in the tests in Table AA below were obtained by appropriate dilutions of the stock suspensions with water.
Into 13.5 centimeter diameter plastic pots containing a potting soil mix, i.e., one-third sandy loam soil, one-third peat moss and one-third perlite by volume, were sown three snapbean seeds (Phaseolus vulgaris var. Cranberry). Five to seven days after planting, the plants were thinned to one plant per pot. Ten to twelve days after planting at the time of full expansion of the primary leaves, each concentration of the test compounds (each pot sprayed with 5 milliliters of solution) was applied to three snapbean plants as a foliar spray by use of an aspirated spray apparatus set at 10 psig air pressure. As a control, a water-acetone solution containing no test compound was also sprayed on three snapbean plants. When dry, all of the plants were placed in a greenhouse at a temperature of 80°F± 5°F and humidity of 50 percent ± 5 percent. At 24 hours and 48 hours after treatment, leaf diffusion resistance in seconds/centimeter (sec/cm) and transpiration rate in micrograms of water/square centimeter second (μg H2O/cm2 · sec) were determined using a LI-COR 1600 steady-state porometer commercially available from Li-Cor, Inc./Li-Cor, Ltd., Lincoln, Nebraska. The values obtained for each test compound concentration and control were averaged to obtain the results in Table AA. TABLE AA
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion
Resistance and Transpiration Rate
Compound Leaf Diffusion Transpiration Rate
No. Resistance (sec/cm) (μg H2O/cm2. sec)
1840 ppm Control 1840 ppm Control
1 13.8 3.3 0.3 1.4
2 14.0 6.0 1.3 3.3
3 12.1 3.4 0.8 2.3
4 15.5(c) 5.6 0.6(c) 2.2
5 7.8 4.8 1.2 1.9 6 16.5 4.3 0.5 1.7
7 11.0 5.5 0.6 1.2
8 14.0 3.3 0.5 1.7 9 7.5 6.0 0.8 1.0 10 4.6 2.2 0.8 1.5 11 4.6 2.2 0.8 1.6 12 4.8(c) 2.5 0.8(c) 1.2 13 12.7 7.6 1.0 1.5 14 4.9 2.9 0.8 1.2 15 25.8 5.0 0.4 1.6 16 18.0 5.7 0.5 1.5 17 11.1 5.8 0.8 1.3 18 9.4 4.9 1.0 2.2 19 9.9 6.0 0.8 1.3 20 18.0 5.4 0.7 2.1 21 8.7 1.7 1.1 5.0 22 8.9 2.8 1.0 2.9 23 13.6 4.7 0.8 2.0 24 24.9(b) 4.6 0.4(b) 1.8 25 26.5 5.8 0.6 2.5 TABLE AA (Cont.)
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion
Resistance and Transpiration Rate
Compound Leaf Diffusion Transpiration Rate
No. Resistance (sec/cm) (μg H2O/cm2. sec)
1840 ppm Control 1840 ppm Control
26 24.8 6.2 0.4 1.9 27 6.9(b) 2.2 2.3(b) 6.5
28 5.9 1.9 2.6 5.9 29 13.8 4.3 0.8 2.9 30 30.7 3.7 0.4 2.8 31 28.2 6.1 0.6 2.6 32 16.6 3.4 0.9 3.6 33 11.8 6.4 0.9 1.7 34 10.7 5.6 0.7 1.2 35 12.9(b) 5.7 0.5(b) 1.3 36 7.2 3.8 0.9 1.6 37 6.7 3.8 0.6 1.0 38 4.4 2.5 0.7 1.4 39 5.1 2.5 0.7 1.4 40 7.6 3.0 0.6 1.5 41 3.6 3.0 1.0 1.4 42 14.6 4.0 0.4 1.5 43 13.7 9.3 0.6 0.9 44 16.7 4.3 1.0 3.5 45 6.6 5.9 1.7 1.8 46 9.3 3.3 2.3 4.0 47 25.6 3.8 0.7 4.1 TABLE AA (Cont.)
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion
Resistance and Transpiration Rate
Compound Leaf Diffusion Transpiration Rate
No. Resistance (sec/cm) (μg H2O/cm2. sec)
1840 ppm Control 1840 ppm Control
48 10.1(b) 9.4 0.8(b) 0.9 49 10.2 9.1 1.1 1.3 50 9.3 4.8 1.0 1.9 51 15.8 5.6 0.5 1.5 52 13.2 3.3 1.8 3.4 53 11.6 4.4 0.5 1.3 54 7.8 2.4 1.0 3.3 55 8.4 4.3 1.1 3.3 56 16.1 6.2 1.0 2.5 57 6.4 2.1 1.3 3.7 58 3.8 2.8 1.7 2.3 59 8.2 2.8 0.8 2.2 60 3.9 1.8 2.1 3.8 61 9.5 5.6 0.9 1.5 62 15.4 5.5 0.6 1.5 63 8.5 6.9 1.1 1.4 64 8.7 4.2 1.6 3.3 65 21.7 13.9 0.4 0.8 66 11.2(c) 8.5 0.7(c) 0.8 67 10.7 8.1 0.7 0.9 68 5.2 4.4 1.2 1.4 69 12.1 4.4 0.5 1.3 TABLE AA (Cont.)
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion Resistance and Transpiration Rate
Compound Leaf Diffusion Transpiration Rate
No. Resistance (sec/cm) (Ma H2O/cm2. sec) 1840 ppm Control 1840 ppm Control
70 3.4 2.2 0.8 1.3
71 2.5 2.0 1.4 1.6
72 14.4 2.1 1.4 4.3
73 5.4 3.6 1.4 2.0
74 5.0(b) 3.2 0.9(b) 1.4
75 10.3 6.3 1.3 1.8
76 12.7 7.4 1.0 1.7
77 13.5 4.4 0.6 1.9
78 10.3 3.7 1.1 2.8
79 19.8 5.3 0.4 1.4
80 14.4(c) 7.6 0.8(c) 1.5
81 10.1(c) 4.7 1.0(c) 2.0
82 19.0 6.1 0.5 1.3
83 26.7 6.5 0 3 1.2
84 7.4(c) 6.5 1.1(c) 1.3
85 13.4 9.2 1.0 1.6
86 6.8 4.0 1.1 1.5
87 14.8 4.3 0.9 2.8
88 6.5 6.8 1.0 1.2
89 11.4(b) 9.7 1.0(b) 1.2 90 10.4(e) 5.8 1.2(e) 2.0 91 4.8 3.3 1.6 2.2 TABLE AA (Cont.)
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion
Resistance and Transpiration Rate
Compound Leaf Diffusion Transpiration Rate
No. Resistance (sec/cm) (μg H2O/cm2. sec)
1840 ppm Control 1840 ppm Control
92 9.5 3.9 0.7 1.6 93 8.1 3.5 0.9 2.0 94 12.0 6.8 0.8 1.3 95 10.0(b) 6.4 0.9(b) 1.4 96 10.0 6.5 1.0 1.4 97 3.1 1.7 1.6 2.1 98 2.7 1.3 1.4 2.6 99 17.1 9.9 0.5 0.9
100 6.2 4.3 1.3 1.8
101 15.2(b) 7.9 0.7(b) 1.3
102 13.3(b) 4.7 0.9(b) 2.0
103 10.5(b) 5.5 1.8(b) 2.5
104 8.6 2.1 1.2 4.2
105 9.9 5.4 0.9 1.6
106 12.3 10.1 1.0 1.3
107 7.4 2.4 0.5 1.4
108 22.8 9.5 0.4 1.0
109 7.1 5.1 1.4 2.0
110 14.2(b) 6.3 0.7(b) 1.4
111 11.2 5.7 0.8 1.4
112 10.9 6.7 1.0 1.6
113 13.3(b) 5.6 0.6(b) 1.3 TABLE AA (Cont.)
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion Resistance and Transpiration Rate
Compound Leaf Diffusion Transpiration Rate
No. Resistance (sec/cm) (μg H2O/cm2. sec)
1840 ppm Control 1840 ppm Control
114 15.0(b) 6.0 0.6(b) 1.4 115 8.0 6.6 0.9 1.1 116 8.6 7.0 1.2 1.7 117 13.5 3.6 0.7 2.2 118 3.3 2.0 1.2 1.8 119 8.7 7.1 0.6 0.8 120 10.1 9.8 1.1 1.3 121 11.4 5.7 0.7 1.3 122 8.7(b) 6.6 0.8(b) 1.4 123 1.9 1.0 2.4 3.9 124 1.8(b) 1.3 2.3(b) 2.6 125 8,9 6.6 0.8 1.1 126 6.2 5.8 1.2 1.3 127 7.9 5.4 1.0 1.4 128 12.4 5.8 0.7 1.6 129 5.1 4.2 1.1 1.4 130 6.8 5.0 0.8 1.0 131 11.2 5.0 0.6 1.3 132 12.6(c) 7.3 0.9(c) 1.5 133 6.6 4.3 1.3 2.0 134 11.0 8.4 1.3 1.5 135 9.7 8.3 1.2 1.5 TABLE AA (Cont.)
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion
Resistance and Transpiration Rate
Compound Leaf Diffusion Transpiration Rate No. Resistance (sec/cm) (μg H2O/cm2. sec)
1840 ppm Control 1840 ppm Control
136 3.9 3.7 2.4 2.6
137 6.4(c) 5.7 1.3(c) 1.4
138 6.7(c) 2.6 0.6(c) 1.4
139 7.7(c) 5.3 1.0(c) 1.5
140 8.8 7.1 1.5 1.8
141 10.8(c) 6.2 0.7(c) 1.2
142 8.4(c) 6.7 1.3(c) 1.8
143 6.5 5.2 1.3 1.7
144 8.1 4.9 0.9 1.4
145 12.6(c) 8.6 0.8(c) 1.1
146 8.4 8.2 1.1 1.2
147 7.8 4.8 1.1 1.7
148 11.1(c) 7.4 0.5(c) 0.8
149 6.3(c) 5.4 1.4(c) 1.6
150 5.5(c) 4.6 1.4(c) 1.6
151 8.3 6.1 1.7 2.3
152 12.7(c) 6.5 ) 0.7(c) 1.3
153 14.9 2.3 0.6 3.5
154 9.4(b) 8.1 0.8(b) 1.0
155 28.4(b) 6.7 0.3(b) 1.1
156 12.0c 5.8 0.6 1.2
157 9.5 2.2 0.6 1.9 TABLE AA (Cont.)
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion
Resistance and Transpiration Rate
Compound Leaf Diffusion Transpiration Rate
No. Resistance (sec/cm) (μg H2O/cm2. sec)
1840 ppm Control 1840 ppm Control
158 10.8 5.0 0.6 1.3 159 6.3 1.9 0.7 1.6 160 6.5 4,4 0.9 1.4 161 17.2 8.2 0.3 0.8 162 4.3(a) 3.4 0.9(a) 1.2 163 3.2(a) 2.6 1.0(a) 1.3 164 4.6 4.4 2.3 2.4 165 4.0 3.6 2.5 2.9 166 5.6(d) 4.9 1.1(d) 1.3 167 9.9 9.7 1.2 1.3 168 4.2 3.5 2.2 2.7 169 5.4 5.2 1.9 2.1 170 6.8 3.1 1.2 3.0 171 6.4 5.2 1.2 1.5 172 11.2 8.1 1.1 1.4 173 22.2 4.9 0.5 2.0 174 10.6 6.3 0.8 1.9 175 6.4 4.2 1.8 2.6 176 6.3 4.9 2.1 2.6 177 7.3 6.6 1.4 1.6 178 38.0 5.5 0.5 3.1 179 12.4 4.8 1.1 2.3 TABLE AA (Cont.)
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion
Resistance and Transpiration Rate
Compound Leaf Diffusion Transpiration Rate
No. Resistance (sec/cm) (μg H2O/cm2. sec)
1840 ppm Control 1840 ppm Control
180 7.3 6.9 1.7 1.8 181 10.8 5.4 2.0 2.7 182 5.7 3.5 2.0 3.5 183 16.6 8.5 1.0 2.0 184 7.1 4.0 1.0 1.8 185 5.4 4.9 1.9 2.0 186 7.3 5.8 1.7 2.3 187 6.7 2.6 1.1 3.7 188 8.7 4.7 1.6 2.6 189 11.5 5.7 1.6 2.6 190 2.7 2.5 3.1 3.3 191 12.3 6.4 1.1 1.7 192 15.0 9.3 1.1 1.8 193 5.2 4.0 1.4 1.9 194 3.7 2.5 2.5 3.5 195 9.5 3.9 1.3 2.6 196 14.1 2.2 0.9 4.6 197 23.1 3.3 0.7 5.1 198 19.2 1.8 0.7 5.2 199 17.1 3.7 0.9 4.0 200 8.2 2.5 1.3 3.9 201 20.4 3.8 0.8 3.7 TABLE AA (Cont.)
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion
Resistance and Transpiration Rate
Compound Leaf Diffusion Transpiration Rate No. Resistance (sec/cm) (μg H2O/cm2. sec)
1840 ppm Control 1840 ppm Control
202 9.5 3.5 2.0 4.3
203 19.7 8.8 0.7 1.7 204 30.3 4.1 0.6 3.5
205 7.7 6.2 1.4 1.7
206 9.3 6.0 1.4 2.0
207 20.9 6.6 0.6 1.7
208 13.5 4.8 1.1 3.0
209 8.1 5.4 1.1 2.0
210 7.1 5.4 1.7 2.3
211 6.0 (c) 5.6 2.3 (c) 2.5
212 7.8 (b) 4.5 1.6 (b) 2.7
213 6.0 (b) 5.9 2.0 (b) 2.1
214 9.3 7.1 1.2 1.6
215 6.6 5.5 1.0 1.3
216 7.9 5 8 1.4 1.9
217 5.9 4.6 1.7 2.1
218 7.5 4.6 1.5 2.0
219 8.3 3.1 1.8 4.6
220 14.0 4.6 0.8 2.3
221 10.6 5.5 1.2 2.4
222 23.0 6.9 0.5 1.6
223 9.9 5.6 1.3 2.1
224 9.4 3.8 1.7 3.7 TABLE AA (Cont.)
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion
Resistance and Transpiration Rate
Compound Leaf Diffusion Transpiration Rate No. Resistance (sec/cm) (μg H2O/cm2. sec)
1840 ppm Control 1840 ppm Control
225 6.7 5.7 2.4 3.1 226 9.6 6.9 1.7 2.2 227 8.4 (b) 6.7 1.8 (b) 2.3 228 31.1 5.7 0.5 2.3 229 25.0 3.6 0.4. 2.5 230 25.1 6.7 0.5 1.6 231 5.9 2.1 1.9 4.3 232 6.9 3.8 2.8 4.0 233 11.8 4.2 1.6 4.4 234 15.4 (b) 3.7 0.9 (b) 3.3 235 12.6 3.1 1.0 4.0 236 6.7 5.3 1.7 2.1 237 21.8 2.6 0.7 5.1 238 3.7 2.6 2.9 3.9 239 25.1 2.6 0.8 4.4 240 11.4 5.5 1.3 2.7 241 11.2 (c) 3.6 1.3 (c) 3.5 242 11.5 2.1 1.3 6.2 243 18.3 5.6 0.6 1.8 244 11.5 2.9 0.4 1.4 245 10.8 3.4 1.4 3.9 246 11.4 3.0 1.1 3.9 247 10.4 2.6 1.5 5.2 TABLE AA (Cont.)
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion
Resistance and Transpiration Rate
Compound Leaf Diffusion Transpiration Rate
No. Resistance (sec/cm) (μg H2O/cm2.sec)
1840 ppm Control 1840 ppm Control
248 3.8 2.5 1.1 1.6
249 3.1 2.8 3.9 4.3
250 2.6 1.9 6.0 8. 2
251 3.3 2.8 3.8 4.1
252 5.1 4.1 2.3 2.9
253 3.3 (b) 2.7 3.5 (b) 4.1
254 5.4 4.2 1.5 2.0
255 5.0 3.8 2.0 2.9
256 4.3 2.2 3.2 5.5
257 28.8 3.9 0.5 3.4
258 2.9 2.7 4.0 4.7
259 14.2 4.7 0.7 1.9
260 30.1 2.9 0.4 3.2
261 10.4 3.2 0.4 1.2
262 17.8 2.8 0.5 3.6
263 10.2 3.3 0.4 1.2
264 22.8 4.6 0.6 2.7
265 3.7 2.6 2.5 3.5
266 14.3 5.7 1.2 2.9
267 12.0 4.1 1.0 2.4
268 6.1 2.6 3.2 6.7
269 11.3 6.9 1.7 2.6
270 19.5 6.4 0.9 2.6 TABLE AA (Cont.)
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion
Resistance and Transpiration Rate
Compound Leaf Diffusion Transpiration Rate No. Resistance (sec/cm) (μg H2O/cm2. sec) 1840 ppm Control 1840 ppm Control
271 19.5 (c) 7.9 0.9 (c) 2.4 272 18.6 4.7 0.9 3.5 273 18.8 5.1 0.8 3.1 274 21.8 4.9 0.8 3.3 275 6.9 3.3 1.6 3.2 276 5.3 4.3 2.2 2.9 277 5.9 (c) 3.5 3.0 (c) 3.4 278 11.0 4.5 1.8 2.7 279 14.6 4.0 0.9 2.8 280 17.6 3.1 0.6 3.4 281 14.8 5.3 0.9 2.3 282 12.4 3.3 1.1 3.1 283 9.3 3.7 1.8 4.4 284 8.8 (d) 3.9 1.5 (d) 3.0 285 13.9 2.4 1.0 5.5 286 9.7 2.0 1.2 5.1 287 5.6 2.4 0.7 1.5 288 6.2 3.4 2.2 3.8 289 3.5 2.8 3.3 4.3 290 9.0 6.2 2.0 2.7 291 2.1 1.9 1.4 1.5 292 23.8 (b) 6.2 0.6 (b) 2.3 293 4.8 (c) 4.4 2.3 (c) 2.4 TABLE AA (Cont.)
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Leaf Diffusion
Resistance and Transpiration Rate
Compound Leaf Diffusion Transpiration Rate No. Resistance (sec/cm) (μg H2O/cm2. sec) 1840 ppm Control 1840 ppm Control
294 31.5 9.3 0.5 1.8
295 28.3 (c) 7.5 0.5 (c) 1.4
296 27.6 6.7 0.5 2.0
(a) Treated at 115 parts per million.
(b) Treated at 230 parts per million.
(c) Treated at 460 parts per million.
(d) Treated at 920 parts per million.
(e) Treated at 3220 parts per milli.on.
The results in Table AA demonstrate that representative heterocyclic nitrogen-containing compounds used in the method of this invention significantly increase leaf diffusion resistance and decrease transpiration rate relative to untreated controls.
Example CLXXI
Water-Use Efficiency of
Representative Heterocyclic Nitrogen-Containing Compounds
Water-use efficiency (WUE) is a determination of both the effectiveness of an antitranspirant compound, i.e., control of water usage by plants, and also the effect of such compound on plant growth, i.e., effect on plant photosynthesis. In particular. WUE is defined as the unit of plant dry matter produced per unit of water utilized for a given time period. As used in Tables BB through FF below, WUE was determined according to the following general procedure:
Solutions of the compounds identified in Tables BB through FF were prepared by dissolving 62.5 milligrams of the test compound into 5 milliliters of acetone. Two, one and 0.5 milliliters of this solution were placed into separate tubes, acetone was added to each tube to a total volume of 12 milliliters and water was then added to each tube to a final volume of 20 milliliters. Final concentrations of test compound in the above stock solutions were 1250 parts per million, 625 parts per million and 312 parts per million by weight. The other concentrations in parts of the test compound per million parts by weight of final solution employed in the tests described hereinbelow were obtained by appropriate dilutions of the stock solutions with water. Into 10.2 centimeter diameter plastic pots containing a potting soil. i.e., one-third sandy loam soil, one-third peat moss and one-third perlite by volume, were sown 12 milligrams of Kentucky bluegrass seeds or tall fescue turfgrass seeds. The plastic pots and potting soil were each weighed before sowing the seeds. The bluegrass and turfgrass were allowed to grow for a period of 8 to 12 weeks after planting and the height of the grasses was maintained at 2.5-3.8 centimeters during this period. Twelve hours prior to application of the test compounds identified in Tables O through S, the bluegrass and turfgrass were clipped to a uniform height of 2.5-3.8 centimeters, and the weight of each pot was obtained prior to treatment. Each concentration of the test compounds including the controls was applied by spraying to four pots (each pot sprayed with 5 milliliters of solution) by use of an aspirated spray apparatus set at 10 psig air pressure. As a control, a water-acetone solution containing no test compound was also applied to four pots. When dry, all of the pots were placed in a greenhouse at a temperature of 80°F + 5°F and humidity of 50 percent ± 5 percent for a 7 day period with no watering. All pots were weighed every 24 hours and the amount of water utilized was determined by calculation using the daily weights and the initial weights. At the end of the 7 day period, visual observations were made of the grasses in all pots. The grasses were then clipped to a uniform height and the clippings were collected, dried and weighed for each pot. Water use was calculated using the following equation: grams of H2O utilized by treated Water use = grasses
(% of Control) grams of H2O ultilized by untreated grasses (control)
WUE was calculated using the following equation:
milligrams of dry weight of
WUE = clippings grams of water utilized
The WUE was standardized to the control for each of. the tests using the following equation:
WUE for treated grasses WUE Index =
WUE for untreated grasses (control)
The values obtained for each test compound concentration and control were averaged to obtain the results in Tables BB through FF.
TABLE BB
Water-Use Efficiency of Representative
Heterocyclic Nitrogen-Containing
Compounds on Kentucky Bluegrass
Compound Concentration Water Use
No. (ppm) (% of Control) WUE WUE Index
Control 100 0.59 1.00
28 312 55 1.45 2.46 625 57 2.04 3.46
1250 54 2.59 4.39
30 312 62 1.25 2.12 625 64 1.53 2.59
1250 65 1.33 2.25
44 312 66 1.76 2.98 625 48 2.40 4.07
1250 35 4.05 6.86
TABLE CC
Water-Use Efficiency of Representative
Heterocyclic Nitrogen-Containing
Compounds on Kentucky Bluegrass
Compound Concentration Water Use
No. (ppm) (% of Control) WUE WUE Index
Control - 100 0.78 1.00
Atrazine* 39 48 1.42 1.82
78 36 1.34 1.72
156 37 0.44 0.56
312 36 0.31 0.40
26 312 63 2.49 3.19 625 59 1.72 2.21
1250 65 1.20 1.54
44 312 41 3.07 3.94 625 39 3.56 4.56
1250 36 3.51 4.50
*Grass damaged at all concentrations; nearly all grass dead at concentrations greater than 78 parts per million; substantial phytotoxi.city. TABLE DD
Water-Use Efficiency of Representative
Heterocyclic Nitrogen-Containing
Compounds on Kentucky Bluegrass
Compound Concentration Water Use
No. (ppm) (% of Control) WUE WUE Index
Control - 100 2.47 1.00
Atrazine* 10 65 2.87 1.03
20 64 2.42 1.16
39 65 2.65 0.98
32 312 89 2.65 1.07 625 81 2.85 1.15
1250 87 3.00 1.21
44 625 58 3.70 1.50 938 52 4.38 1.77
1250 49 3.94 1.59
64 312 86 2.54 1.03 625 87 2.47 1.00
1250 86 2.73 1.11
*Grass damaged at all concentrations; substantial phytotoxiciyy. TABLE EE
Water-Use Efficiency of Representative
Heterocyclic Nitrogen-Containing
Compounds on Kentucky Bluegrass
Compound Concentration Water Use
No. (ppm) (% of Control) WUE WUE Index
Control - 100 3.90 1.00
44 625 49.0 8.00 2.05 938 41.3 12.0 3.08
54 312 63.9 7.00 1.79 625 63.1 6.50 1.67
TABLE FF
Water-Use Efficiency of Representative
Heterocyclic Nitrogen-Containing
Compounds on Tall Fescue Turfgrass
Compound Concentration Water Use
No. (ppm) (% of Control) WUE WUE Index
Control - 100 0.74 1.00
Atrazine* 5 81 1.26 1.70
10 83 1.09 1.47
20 106 0.80 1.35
18 312 62 1.28 1.60 625 61 2.02 2.73
1250 57 1.75 2.36
44 625 78 1.56. 2.11
1250 54 2.04 2.76
101 312 96 1.77 2.39 625 58 0.99 1.34
1250 52 1.86 2.51
*Grass damaged at all concentrations; substantial phytotoxicity. The results in Tables BB through FF demonstrate that representative heterocyclic nitrogen-containing compounds used in the method of this invention significantly decrease water use relative to untreated controls with no negative effect on plant growth, i.e., no negative effect on plant photosynthesis. In contrast, the treatment of grasses with atrazine caused substantial phytotoxicity.
Example CLXXII
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on
Crop Yield Enhancement - Corn
Agronomic uses of compounds having antitranspirant activity include not only water conservation but also crop yield enhancement. As an illustration, an antitranspirant compound applied to a crop may increase actual crop yields by reducing water loss during periods of critical water need. As used in Table GG below, crop yield enhancement was determined for corn according to the following general procedure:
Solutions of Compound 44 were prepared by dissolving either 0.78 grams. 1.55 grams or 3.10 grams of the compound into 780 milliliters of acetone. Just prior to the time of application, water was added to each of the above solutions to a final volume of 1300 milliliters. Solutions of a control having no test compound were also prepared by mixing 780 milliliters of acetone and 520 milliliters of water to a total volume of 1300 milliliters.
The above formulations were applied to corn by utilizing a statistical treatment procedure involving 42 separate plots. Each plot consisted of 4 rows individually 20 feet in length and about 3 feet between rows. Each experiment was designed as a randomized complete block of six different repetitions in which each repetition included the following: (1) treatment with control having no test compound; (2) treatment with 0.78 grams/plot of Compound 44 at time T1 designated in Table GG; (3) treatment with 1.55 grams/plot of Compound 44 at time T1 designated in Table GG; (4) treatment with 3.10 grams/plot of Compound 44 at time T1 designated in Table GG; (5) treatment with 0.78 grams/plot of Compound 44 at time T2 designated in
Table GG; (6) treatment with 1.55 grams/plot of
Compound 44 at time T2 designated in Table GG; and
(7) treatment with 3.10 grams/plot of Compound 44 at time T2 designated in Table GG. The above formulations were applied to each plot by use of a carbon dioxide backpack sprayer set at about 20-40 psig air pressure. The planting, application and harvesting times for the corn crop are detailed in Table GG. The harvested corn crop for yield determination included the inner 10 feet of the middle 2 rows in each plot (5 feet in from ends of the middle 2 rows). Water stress conditions existed to a degree during at least a portion of the growing period. The values obtained for each plot in each repetition were averaged to obtain the results in Table GG.
TABLE GG
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on
Crop Yield Enhancement-Corn
Compound Concentration Actual Yield
No. (gm/plot) Application Timing* (kg/plot)
Control - - 9.87
44 0.78 Tassel (T1) 10.71
1.55 Tassel (T1) 10.62
3.10 Tassel (T1) 10.39
44 0.78 3 Weeks after Tassel (T2) 11.17
1.55 3 Weeks after Tassel (T2) 11.18
3.10 3 Weeks after Tassel (T2) 10.30
*First application at tassel (T1), 46 days after planting; second application at 3 weeks after tassel (T2), 67 days after planting; and harvesting occurred 114 days after planting.
The results in Table GG demonstrate that treatment of corn with a representative heterocyclic nitrogen-containing compound, i.e., Compound 44, in accordance with the method of this invention significantly increases corn crop yield in comparison with untreated control corn crops at similar conditions.
Example CLXXIII Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Crop Yield Enhancement - Cotton Agronomic uses of compounds having antitranspirant activity include not only water conservation but also crop yield enhancement. As an illustration, an antitranspirant compound applied to a crop may increase actual crop yields by reducing water loss during periods of critical water need. As used in Table HH below, crop yield enhancement was determined for cotton according to the following general procedure:
Solutions of Compound 44 were prepared by dissolving either 0.78 grams. 1.55 grams or 3.10 grams of the compound into 780 milliliters of acetone. Just prior to the time of application, water was added to each of the above solutions to a final volume of 1300 milliliters. Solutions of a control having no test compound were also prepared by mixing 780 milliliters of acetone and 520 milliliters of water to a total volume of 1300 milliliters.
The above formulations were applied to cotton by utilizing a statistical treatment procedure involving 36 separate plots. Each plot consisted of 4 rows individually 20 feet in length and about 3 feet between rows. Each experiment was designed as a randomized complete block of six different repetitions in which each repetition included the following: (1) treatment with control having no test compound; (2) treatment with 0.78 grams/plot of Compound 44 at time T1 designated in Table HH; (3) treatment with 1.55 grams/plot of Compound 44 at time T1 designated in Table HH; (4) treatment with 3.10 grams/plot of Compound 44 at time T1 designated in Table HH; (5) treatment with 0.78 grams/plot of Compound 44 at time T2 designated in Table HH; and (6) treatment with 3.10 grams/plot of Compound 44 at time T2 designated in Table HH. The above formulations were applied to each plot by use of a carbon dioxide backpack sprayer set at about 20-40 psig air pressure. The planting, application and harvesting times for the cotton crop are detailed in Table HH. The harvested cotton crop for yield determination included the inner 10 feet of the middle 2 rows in each plot (5 feet in from ends of the middle 2 rows). Water stress conditions existed to a degree during at least a portion of the growing period. The values obtained for each plot in each repetition were averaged to obtain the results in Table HH.
TABLE HH
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on
Crop Yield Enhancement-Cotton
Compound Concentration Actual Yield
No. (gm/plot) Application Timing* (gm/plot)
Control - - 984.5
44 0.78 Bloom (T1) 1081.0
1.55 Bloom (T1) 1160.4
3.10 Bloom (T1) 1175.3
44 0.78 3 Weeks after Bloom (T2) 1057.8
3.10 3 Weeks after Bloom (T2) 1065.1
*First application at bloom (T1), 47 days after planting; second application at 3 weeks after bloom (T2), 67 days after planting; and harvesting occurred 126 days after planting.
The results in Table HH demonstrate that treatment of cotton with a representative heterocyclic nitrogen-containing compound, i.e., Compound 44, in accordance with the method of this invention significantly increases cotton crop yield in comparison with untreated control cotton crops at similar conditions.
Example CLXXIV
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on
Crop Yield Enhancement - Sweet Potatoes
Agronomic uses of compounds having antitranspirant activity include not only water conservation but also crop yield enhancement. As an illustration, an antitranspirant compound applied to a crop may increase actual crop yields by reducing water loss during periods of critical water need. As used in Table II below, crop yield enhancement was determined for sweet potatoes according to the following general procedure:
Solutions of Compound 44 were prepared by dissolving either 0.78 grams, 1.55 grams or 3.10 grams of the compound into 780 milliliters of acetone. Just prior to the time of application, water was added to each of the above solutions to a final volume of 1300 milliliters. Solutions of a control having no test compound were also prepared by mixing 780 milliliters of acetone and 520 milliliters of water to a total volume of 1300 milliliters.
The above formulations were applied to sweet potatoes by utilizing a statistical treatment procedure involving separate plots. Each plot consisted of 4 rows individually 20 feet in length and about 3 feet between rows. Each experiment was designed as a randomized complete block of six different repetitions in which each repetition included the following: (1) treatment with control having no test compound: (2) treatment with 0.78 grams/plot of Compound 44 at time T1 designated in Table II; (3) treatment with 1.55 grams/plot of Compound 44 at time T1 designated in Table II; (4) treatment with 3.10 grams/plot of Compound 44 at time T1 designated in Table II; (5) treatment with 0.78 grams/plot of Compound 44 at time T2 designated in Table II; and (6) treatment with 1.55 grams/plot of Compound 44 at time T2 designated in Table II. The above formulations were applied to each plot by use of a carbon dioxide backpack sprayer set at about 20-40 psig air pressure. The planting, application and harvesting times for the sweet potatoe crop are detailed in Table II. The harvested sweet potatoe crops for yield determination included the inner 10 feet of the middle 2 rows in each plot (5 feet in from ends of the middle 2 rows). Water stress conditions existed to a degree during at least a portion of the growing period. The values obtained for each plot in each repetition were averaged to obtain the results in Table II.
TABLE II Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Crop Yield Enhancement-Sweet Potatoes
Compound Concentration Actual Yield
No. (gm/plot) Application Timing* (kg/plot)
Control - - 95.48
44 0.78 Tuber Initiation (T1) 111.10
1.55 Tuber Initiation (T1) 99.88
3.10 Tuber Initiation (T1) 99.88
44 0.78 4 Weeks after Tuber 107.36
Initiation (T2)
1.55 4 Weeks after Tuber 98.78 Initiation (T2)
*First application at tuber initiation (T1), 43 days after transplanting; second application at 4 weeks after tuber initiation (T2), 77 days after transplanting; and harvesting occurred 140 days after transplanting. The results in Table II demonstrate that treatment of sweet potatoes with a representative heterocyclic nitrogen-containing compound, i.e., Compound 44, in accordance with the method of this invention significantly increases sweet potatoe crop yield in comparison with untreated control sweet potatoe crops at similar conditions.
Example CLXXV
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on
Crop Yield Enhancement - Soybeans
Agronomic uses of compounds having antitranspirant activity include not only water conservation but also crop yield enhancement. As an illustration, an antitranspirant compound applied to a crop may increase actual crop yields by reducing water loss during periods of critical water need. As used in Table JJ below, crop yield enhancement was determined for soybeans according to the following general procedure:
Solutions of Compound 44 were prepared by dissolving either 0.78 grams, 1.55 grams or 3.10 grams of the compound into 780 milliliters of acetone. Just prior to the time of application, water was added to each of the above solutions to a final volume of 1300 milliliters. Solutions of a control having no test compound were also prepared by mixing 780 milliliters of acetone and 520 milliliters of water to a total volume of 1300 milliliters.
The above formulations were applied to soybeans by utilizing a statistical treatment procedure involving 36 separate plots. Each plot consisted of 4 rows individually 20 feet in length and about 3 feet between rows. Each experiment was designed as a randomized complete block of six different repetitions in which each repetition included the following: (1) treatment with control having no test compound: (2) treatment with 1.55 grams/plot of Compound 44 at time T1 designated in Table JJ; (3) treatment with 3.10 grams/plot of Compound 44 at time T1 designated in Table JJ; (4) treatment with 0.78 grams/plot of Compound 44 at time T2 designated in.Table JJ; (5) treatment with 1.55 grams/plot of Compound 44 at time T2 designated in Table JJ; and (6) treatment with 3.10 grams/plot of Compound 44 at time T2 designated in Table JJ. The above formulations were applied to each plot by use of a carbon dioxide backpack sprayer set at about 20-40 psig air pressure. The planting, application and harvesting times for the soybean crop are detailed in Table JJ. The harvested soybean crop for yield determination included the inner 10 feet of the middle 2 rows in each plot (5 feet in from ends of the middle 2 rows). Water stress conditions existed to a degree during at least a portion of the growing period. The values obtained for each plot in each repetition were averaged to obtain the results in Table JJ.
TABLE JJ
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on
Crop Yield Enhancement-Soybeans
Compound Concentration Actual Yield
No. (gm/plot) Application Timing* (kg/plot)
Control - - 0.48
44 1.55 Flowering (T1) 0.55
3.10 Flowering (T1) 0.55
44 0.78 3 Weeks after Flowering (T2) 0.58
1.55 3 Weeks after Flowering (T2) 0.60
3.10 3 Weeks after Flowering (T2) 0.52
*First application at flowering (T1), 63 days after planting; second application at 3 weeks after flowering (T2), 86 days after planting; and harvesting occurred 201 days after planting.
The results in Table JJ demonstrate that treatment of soybeans with a representative heterocyclic nitrogen-containing compound, i.e., Compound 44. in accordance with the method of this invention significantly increases soybean crop yield in comparison with untreated control soybean crops at similar conditions.
Example CLXXVI Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on Crop Yield Enhancement - Cotton and Potatoes
Agronomic uses of compounds having antitranspirant activity include not only water conservation but also crop yield enhancement. As an illustration, an antitranspirant compound applied to a crop may increase actual crop yields by reducing water loss during periods of critical water need. As used in Tables KK and LL below, crop yield enhancement was determined for cotton and potatoes according to the following general procedure:
An emulsifiable concentrate of Compound 44 was prepared containing 39.3 weight percent of propylene carbonate, 39.3 weight percent of Exxate 700 (Exxon Chemicals, Houston, Texas), 10.0 weight percent of Atlox 3455F (ICI Americas, Wilmington, Delaware) and 11.4 weight percent of Compound 44. Just prior to the time of application, 31 milliliters (3.5 grams of Compound 44) or 62 milliliters (7.0 grams of Compound 44) of the above emulsifiable concentrate was added to water to a final volume of 3125 milliliters.
The above formulations were applied to the particular crop designated in Tables KK and LL by utilizing a statistical treatment procedure involving 30 separate plots. Each plot consisted of 4 rows individually 30 feet in length and about 3 feet between rows. Each experiment was designed as a randomized complete block of six different repetitions in which each repetition included the following: (1) treatment with control having no test compound; (2) treatment with 3.5 grams/plot of Compound 44 at time T1 designated in Table KK and LL; (3) treatment with 7.0 grams/plot of Compound 44 at time T1 designated in Tables KK and LL; (4) treatment with 3.5 grams/plot of Compound 44 at time T2 designated in Tables KK and LL; and (5) treatment with 7.0 grams/plot of Compound 44 at time T2 designated in Tables KK and LL. The above formulations were applied to. each plot by use of a carbon dioxide backpack sprayer set at about 20-40 psig air pressure. The planting, application and harvesting times for each crop are detailed in Tables KK and LL. The harvested crops for yield determination included the inner 20 feet of the middle 2 rows in each plot (5 feet in from ends of the middle 2 rows). Water stress conditions existed to a degree during at least a portion of the growing period. The values obtained for each plot in each repetition were averaged to obtain the results in Tables KK and LL.
TABLE KK
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on
Crop Yield Enhancement-Cotton
Compound Concentration Actual Yield
No. (gm/plot) Application Timing* (kg/plot)
Control - - 3.18
44 3.5 Two weeks before Bloom (T1) 3.49
7.0 Two weeks before Bloom (T1) 3.48
44 3.5 Bloom (T2) 3.61
7.0 Bloom (T2) 3.35
*First application at two weeks before bloom (T1), 61 days after planting; second application at bloom (T2), 73 days after planting; and harvesting occurred 167 days after planting.
TABLE LL
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on
Crop Yield Enhancement-Potatoes
Compound Concentration Actual Yield
No. (gm/plot) Application Timing* (kg/plot)
Control - - 9.01
44 3.5 Flowering (T1) 10.94
7.0 Flowering (T1) 10.23
44 3.5 3 Weeks after Flowering 10.30
(T2)
7.0 3 Weeks after Flowering 9.87
(T2)
*First application at flowering (T1) , 75 days after planting; second application at 3 weeks after flowering (T2), 96 days after planting; and harvesting occurred 125 days after planting.
The results in Tables KK and LL demonstrate that treatment of cotton and potatoes with a representative heterocyclic nitrogen-containing compound, i.e., Compound 44, in accordance with the method of this invention significantly increases crop yield in comparison with untreated control crops at similar conditions.
Example CLXXVII
Effect of Representative Heterocyclic Nitrogen-Containing Compounds on Crop Yield Enhancement - Soybeans
Agronomic uses of compounds having antitranspirant activity include not only water conservation but also crop yield enhancement. As an illustration, an antitranspirant compound applied to a crop may increase actual crop yields by reducing water loss during periods of critical water need. As used in Table MM below, crop yield enhancement was determined for soybeans according to the following general procedure:
An emulsifiable concentrate of Compound 44 was prepared containing 39.3 weight percent of propylene carbonate, 39.3 weight percent of Exxate 700 (Exxon Chemicals, Houston. Texas), 10.0 weight percent of Atlox 3455F (ICI Americas. Wilmington, Delaware) and 11.4 weight percent of Compound 44. Just prior to the time of application, 31 milliliters (3.5 grams Compound 44) or 62 milliliters (7.0 grams Compound 44) of the above emulsifiable concentrate was added to water to a final volume of 3125 milliliters.
The above formulations were applied to the soybeans by utilizing a statistical treatment procedure involving 18 separate plots. Each plot consisted of 4 rows individually 30 feet in length and about 3 feet between rows. Each experiment was designed as a randomized complete block of six different repetitions in which each repetition included the following: (1) treatment with control having no test compound; (2) treatment with 3 . 5 grams/plot of Compound 44 at time T1 des ignated in Table MM; and (3) treatment with 7.0 grams/plot of Compound 44 at time T1 designated in Table MM. The above formulations were applied to each plot by use of a carbon dioxide backpack sprayer set at about 20-40 psig air pressure. The planting, application and harvesting times for the soybean crop are detailed in Table MM. The harvested soybean crop for yield determination included the inner 20 feet of the middle 2 rows in each plot (5 feet in from ends of the middle 2 rows). Water stress conditions existed to a degree during at least a portion of the growing period. The values obtained for each plot in each repetition were averaged to obtain the results in Table MM.
TABLE MM
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on
Crop Yield Enhancement-Soybeans
Compound Concentration Actual Yield
No. (gm/plot) Application Timing* (kg/plot)
Control - - 6.29
44 3.5 Flowering (T1) 6.87 7.0 Flowering (T1) 6.50
*First application at flowering (T1), 48 days after planting; and harvesting occurred 186 days after planting.
The results in Table MM demonstrate that treatment of soybeans with a representative heterocyclic nitrogen-containing compound, i.e., Compound 44, in accordance with the method of this invention significantly increases soybean crop yield in comparison with untreated control soybean crops at similar conditions.
Example CLXXVIII
Effect of Representative Heterocyclic Nitrogen-Containing Compounds on Crop Yield Enhancement - Alfalfa
The effect of representative heterocyclic nitrogen-containing compounds on crop yield enhancement was also determined for alfalfa according to the following general procedure:
Solutions of Compound 44 were prepared by dissolving either 6.60 grams or 13.20 grams of the compound into 3300 milliliters of acetone. Just prior to the time of application, water was added to each of the above solutions to a final volume of 5500 milliliters. Solutions of a control having no test compound were also prepared by mixing 3300 milliliters of acetone and 2200 milliliters of water to a total volume of 5500 milliliters.
The above formulations were applied to designated plots of one year old established alfalfa crop by utilizing a self-propelled chemical spray applicator set at 40 psig air pressure. Each plot had the following dimensions: 20 feet in width by 30 feet in length. Each treatment including the controls consisted of 6 replications on 6 separate plots. The above formulations were applied 20 days following a cutting and the alfalfa was harvested 28 days following the treatment. The harvested alfalfa crop for yield determination included a one square meter area from the center of each plot. Water stress conditions existed to a degree during at least a portion of the growing period. The values obtained for each plot in each repetition were averaged to obtain the results in Table NN below.
TABLE NN
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on
Crop Yield Enhancement-Alfalfa
Actual Yield
Compound Concentration Fresh Weight* Dry Weight* No. (gm/plot) (gm/m2) (gm/m2)
Control 301.2 128.2
44 6.60' 331.2 146.7 13.20 342.8 153.2
*Fresh weight was determined by weighing the alfalfa immediately after harvest.
**Dry weight was determined by drying the harvested alfalfa in an oven at 90ºC for 24 hours and then weighing the dried alfalfa.
The results in Table NN demonstrate that treatment of alfalfa with a representative heterocyclic nitrogen-containing compound, i.e., Compound 44, in accordance with the method of this invention significantly increases alfalfa crop yield in comparison with untreated control alfalfa crops.
Example CLXXIX
Effect of Representative Heterocyclic
Nitrogen-Containing Compounds on
Photosynthetic Electron Transport
Because the two photosystems, i.e., Photosystems I and II, involved in plant photosynthesis are interconnected by an electron transport chain, the use of artificial electron donors and acceptors allows the study of specific partial reactions of the light reactions of photosynthesis. In accordance with the procedure described in Brewer, P.E., Arntzen. C.J., and Slife, F.W., Weed Science 27: 300-308 (1979), an isolated chloroplkst assay was used to determine the degree of photosynthetic inhibition caused by the compounds identified in Table OO. In general, the procedure involved osmotically disrupting isolated pea chloroplasts, placing the chloroplasts in a reaction mixture and utilizing methylviologen as the terminal electron acceptor. Oxygen consumption was measured using a Clark electrode attached to a Gilson auxograph. The results in Table OO are reported as percent inhibition compared to an untreated control. TABLE OO
Effect of Representative Heterocyclic Nitrogen-Containing Compounds on Photosynthetic Electron Transport
Compound Concentration Percent Inhibition
No. ( g/liter) ( Oxygen Uptake)
Control 0 0
44 622 0 93 650 0
Atrazine 108 65
Diuron 47 55
The results in Table OO demonstrate that compounds used in this invention cause no inhibition of photosynthetic electron transport whereas atrazine and diuron both cause substantial inhibition of photosynthetic electron transport.
Although the invention has been illustrated by the preceding examples, it is not to be construed as being limited thereby; but rather, the invention encompasses the generic area as hereinbefore disclosed. Various modifications and embodiments can be made without departing from the spirit and scope thereof.

Claims

Claims
1. A method of reducing moisture loss from plants which comprises applying to the plant surface an effective amount, sufficient to reduce moisture loss from the plant surface without substantially inhibiting plant photosynthetic electron transport, of a compound having the formula:
R1 - X - R2
wherein:
R1 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl. alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkyiammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000584_0001
or
or
Figure imgf000584_0002
R1 is a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkypyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3 ,
-X - R3 ,
or
Figure imgf000586_0001
Figure imgf000587_0001
X is a covalent single bond or double bond, a substituted or unsubstituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 , = X-R3,
-X - R3 ,
Figure imgf000589_0001
or and
Figure imgf000589_0002
R2 is a substituted or unsubstituted, heterocyclic ring system having at least one nitrogen atom which is selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylaikylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, aIkylaminothiocarbonyl, diaIkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X R3, = X-R3,
X - R3
or
Figure imgf000591_0001
Figure imgf000591_0002
wherein:
R3 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium, -X, - X, -X = R3 , = X-R3,
-X - R3 ,
Figure imgf000594_0001
or
; or
Figure imgf000594_0002
R3 is a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted. branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphαsphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000596_0001
or
Figure imgf000596_0002
Y1 and Y4 are independently oxygen or sulfur;
Y2 and Y3 are independently oxygen, sulfur, amino or a covalent bond; and
R4 and R5 are independently hydrogen or substituted or unsubstituted alkyl. polyhaloalkyl. phenyl or benzyl in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl. haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 , = X-R3,
-X - R3 ,
Figure imgf000598_0001
or
Figure imgf000598_0002
2. The method of claim 1 wherein R1 and R3 are independently a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system having the formula
Figure imgf000599_0001
a bicyclic aromatic or nonaromatic ring system having the formula selected from
Figure imgf000599_0002
and
Figure imgf000599_0003
a polycyclic aromatic or nonaromatic ring system having the formula selected from
Figure imgf000600_0001
Figure imgf000600_0002
and
Figure imgf000600_0003
and a bridged ring system which may be saturated or unsaturated having the formula selected from
Figure imgf000601_0001
and
Figure imgf000601_0002
Figure imgf000601_0003
wherein: A1 represents a ring-forming chain of atoms which together with B forms a carbocyclic or heterocyclic ring system containing from 0 to 4 double bonds or from 0 to 2 triple bonds; B1 represeits a saturated or unsaturated carbon atom;
A2 and A3 independently represent a ring-forming chain of atoms which together with B2 and B3 form a carbocyclic or heterocyclic ring system; B2 and B3 are independently a saturated or unsaturated carbon atom or a saturated nitrogen atom; A4, A5, A6, and A7 independently represent a ring-forming chain of atoms which together with B4, B5, B6 and B7 form a carbocyclic or heterocyclic ring system; B4, B5, B6 and B7 are independently a saturated or unsaturated carbon atom or a saturated nitrogen atom; A8, A9 and A10 independently represent a ring-forming chain of atoms which together with B8, B9, B10 and B11 form a carbocyclic or heterocyclic ring system; B8, B9 and B10 are independently a saturated or unsaturated carbon atom or a saturated nitrogen atom; B11 represents a saturated or unsaturated carbon atom, nitrogen atom or phosphorous atom; A11, A12 and A13 independently represent a ring-forming chain of atoms which together with B12 and B13 form a carbocyclic or heterocyclic ring system; B12 and B13 are independently a saturated carbon atom or a nitrogen atom; and
Z is the same or different and is one or more of hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000604_0001
or
Figure imgf000604_0002
wherein R3, R4, R5, Y1, Y2, Y3, Y4 and X are as defined in claim 1.
3. The method of claim 1 in which the compound has the formula
Figure imgf000605_0001
wherein:
R'1 is the same or different and is one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000607_0001
or
Figure imgf000607_0002
X'1 is O, S, SO, SO2, NH, CH2, CO, a single covalent bond, CH2O, CH2S, -CH(CH3)O,
-CH(CN)O-, -CH=NO-, -C(CH3) =NO- , -CH2CH2O-,
-CH2CH2-, -CSC-, -CH2SO-, -CH2SO2-,
-OCH2CH2O-, -CH(alkyl)- or -CONH-; and
Y'1 and Y'2 are independently halogen, alkyl or alkoxy; wherein X, R3, R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 1.
4. The method of claim 1 in which the compound has the formula
Figure imgf000608_0001
wherein:
R' and R' are the same or different 2 3 and R'2 is one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl: alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulf inyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, aIkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, ary-l(alkyl) amino, araIkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium, -X, - X, -X - R3, = X-R3,
-X - R3 ,
Figure imgf000610_0001
or
:
Figure imgf000610_0002
X'2 is O, S, SO, SO2, NH, CH2, CO, a single covalent bond. -CH(CH3)O-. -CH(CN)O-. -CH-NO-, -C(CH3)=NO-, -CH2CH2O-, -C≡C-, -CH2SO-, -CH2SO2-, -OCH2CH2O-. -CH(alkyl)- or -CONH-; and
Y'3 is halogen; wherein X, R 3 , R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 1.
5. The method of claim 1 in which the compound has the formula
Figure imgf000610_0003
wherein:
R'4, R'5 and R'6 are the same or different and R'4 is one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, aIkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alfcenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, aIkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium, -X, = X, -X = R3, = X-R3,
-X - R3
Figure imgf000613_0002
or
and
Figure imgf000613_0003
X' is O, S, SO, SO2, NH, CH2, CO, a single covalent bond, -CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-, -CH2CH2O- , -C≡C-, -CH2SO-, -CH2SO2-, -OCH2CH2O-,
-CH(alkyl)- or -CONH-; wherein X, R3, R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 1.
6. The method of claim 1 in which the compound has the formula
Figure imgf000613_0001
wherein: Y'4, Y'5, Y'6, Y'7 and Y'8 are the same or different and are hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl. aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 , = X-R3, -X - R3
Figure imgf000616_0001
or
Figure imgf000616_0002
Y'9, Y'10, Y'11 and Y'12 are the same or different and are hydrogen, halogen, alkyl, polyhaloalkyl, cyano or aryl; m' and n' are the same or different and are a value of from 0 to 5;
X' is O, S, SO, SO2, NH, CH2, CO, a single covalent bond. -CH(CH3)O-. -CH(CN)O-,
-CH=NO-, -C(CH3)=NO-, -CH2CH2O-, -C≡C-,
-CH2SO-, -CH2SO2-, -OCH2CH2O-,
-CH(alkyl)- or -CONH-; and
Y'13 and Y'14 are the same or different and are halogen, alkyl or alkoxy; wherein X, R3, R4, R5, Y1 , Y2, Y3 and
Y4 are as defined in claim 1.
7. The method of claim 1 in which the compound has the formula
Figure imgf000616_0003
wherein: Y'4, Y'5, Y'6, Y'7 and Y'8 are the same or different and are hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium, -X, X, -X = R3, - X-R3,
-X - R3 ,
Figure imgf000619_0001
Figure imgf000619_0002
or
:
Figure imgf000619_0003
Y'9 and Y'10 are the same or different and are hydrogen, halogen, alkyl, polyhaloalkyl, cyano or aryl; m' and n' are the same or different and are a value of from 0 to 5;
X'5 is the same or different and is O, S,
SO, SO2, NH, CH2, CO, a single covalent bond,
-CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3) =NO- ,
-CH2CH2O- -C≡C-, -CH2SO-, -CH2SO -,
-OCH2CH2O-, -CH(alkyl)- or -CONH-;
Y'15 is O or S;
Y'91, and Y'92 are independently halogen; and
X'6 is O or S; wherein X, R3, R4, R5, Y1, Y2, Y3 and Y4 are as defined in claim 1,
8. The method of claim 1 in which the compound has the formula
Figure imgf000620_0001
wherein:
Y'4, Y'5, Y'6, Y'7 and Y'8 are the same as different and are hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts , alkoxycarbonylamino , alkylaminocarbonyloxy , dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocaxhonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000622_0001
Figure imgf000622_0002
or
Figure imgf000622_0003
X'7 is the same or different and is O, S,
SO, SO2, NH, CH2, CO, a single covalent bond,
-CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-,
-CH2CH2O-, -C≡C-, -CH2SO-, -CH2SO2-,
-CH2SO2-, -OCH2CH2O-, -CH(alkyl)- or -CONH-; m' is a value of from 0 to 5;
Y'16 is hydrogen, alkyl, alkylcarbonyl, alicylsulfonyl, or polyhaloalkylsulfonyl; and
Y'93 and Y'94 are independently halogen; wherein X, R3, R4, R5, Y1, Y2, Y3 and Y4 are as defined in claim 1,
9. The method of claim 1 in which the compound has the formula
Figure imgf000623_0001
wherein:
Y'4, Y'5, Y'6, Y'7 and Y'8 are the same or different and are hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhalcalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000625_0001
Figure imgf000625_0002
or
and
Figure imgf000625_0003
Y'95 and Y'96 are independently halogen; wherein X, R3, R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 1,
10. The method of claim 1 in which the compound has the formula
Figure imgf000625_0004
wherein:
Y'19 and Y'21 are the same or different and Y'19 is one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulf onyl , alkylaminosulf onyl , dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, araIkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000627_0001
Figure imgf000627_0002
or
Figure imgf000628_0001
A' is as defined for R1 in claim 1;
X'10 is as defined for X in claim 1; and
Y'20 is halogen, cyano, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, or polyhaloalkylsulfonyloxy; wherein X, R 3 , R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 1,
11. The method of claim 1 in which the compound has the formula
Figure imgf000628_0002
wherein:
R'12 is as defined for R1 in claim 1;
Y'22 is halogen, cyano, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, or polyhaloalkylsulfonyloxy; and
Y'23 is hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfo-nyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium, -X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000630_0001
Figure imgf000630_0002
or
;
Figure imgf000630_0003
wherein X, R 3 , R4, R5, Y1, Y2, Y3 and
Y4 are as defined- in claim 1,
12. The method of claim 1 in which the compound has the formula
Figure imgf000631_0001
wherein: is as defined for R2 in claim 1; and
Y'31 and Y'32 are the same or different and are halogen, alkyl or alkoxy.
13. The method of claim 1 in which the compound has the formula
Figure imgf000631_0002
wherein:
A'2 is as defined for R1 in claim l;
X'12 is as defined for X in claim l; and
Y'33 and Y'34 are the same or different and are halogen, alkyl or alkoxy.
14. The method of claim 1 in which the compound has the formula selected from
Figure imgf000632_0001
wherein
Y'41, Y'42, Y'43, Y'44, Y'45, Y'46, Y'47, Y'48, Y'49, Y'50, Y'51,
Y"48, Y'52, Y'53, Y'54, Y'55, Y'56, Y'57, Y"59, Y'58, Y'59, Y'60, Y'61, and Y'62 are the same or different and Y'41, Y'45, Y'48, Y'56, and Y'59 are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
or
Figure imgf000634_0001
Figure imgf000634_0002
A'4, A'5, A'6, A'7, A'8 and A'9 are as defined for R1 in claim 1; and
X"14, X'15, X'16, X'17, X'18 and
X'19 are the same or different and are O, S, SO,
SO2, NH, CH2, CO, a single covalent bond,
-CH(CH3)O-, -CH(CN)O-, -CH=NO- , -C(CH3)=NO-,
-CH2CH2O-, -C≡C-, -CH2SO-, -CH2SO2.
-OCH2CH2O-, -CH(alkyl)- or -CONH-; wherein X, R 3, R4, R5, Y1, Y2, Y3, and
Y4 are as defined in claim 1,
15. The method of claim 1 in which the compound has the formula
Figure imgf000635_0001
wherein:
A'10 is as defined for R1 in claim 1;
X'20 is as defined for X in claim 1;
A'11 is a substituted or unsubstituted, 5-membered heterocyclic ring system having at least one nitrogen atom in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl) amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000637_0001
Figure imgf000637_0002
or
Figure imgf000637_0003
Y'63 and Y'64 are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000639_0001
Figure imgf000639_0002
or
;
Figure imgf000639_0003
wherein X, R 3, R4, R5, Y1 , Y2, Y3 and
Y4 are as defined in claim 1.
16. The method of claim 1 in which the compound has the formula selected from
Figure imgf000640_0001
wherein: Y'65, Y'66, Y' 67, Y'68, Y'69, Y'70, Y'71, Y'72, Y'73, Y'74, Y'75,
Y' 76 Y' 77, Y' 78, Y' 79, Y' 80 and Y' 81 are the same or different and Y'67, Y'70,
Y'73, Y'76 and Y'79 are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triirylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl: alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isccyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X - R3, = X-R3,
-X - R3 ,
Figure imgf000642_0001
Figure imgf000642_0002
or
Figure imgf000643_0001
r' is a value of 0 or 1; A'12, A'13, A'14, A'15, A'16 and are as defined for R1 in claim 1, and
X'21, X'23, X'24, X'25 and
X'26 are as defined for X in claim 1; wherein X, R3, R4, R5, YY1l*, YY22', Y3 and Y4 aare as defined in claim 1.
17. The method of claim 1 in which the compound has the formula
Figure imgf000643_0002
wherein: Y'82, Y'83, Y'84, Y'85 and R'17 are the same or different and are hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000645_0002
Figure imgf000645_0001
or
; a
Figure imgf000645_0003
X' is as defined for X in claim 1; 27 wherein X, R3, R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 1,
18. The method of claim 1 in which the compound has the formula selected from
Figure imgf000646_0001
wherein:
R'18 and Y'90 are the same or different and Y'18 is one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl: alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 , = X-R3,
-X - R3 ,
Figure imgf000648_0001
Figure imgf000648_0002
or
Figure imgf000648_0003
18 is as defined for R1 in claim 1; and
X'29 is as defined for X in claim 1; wherein X, R 3 , R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 1,
19. The method of claim 1 in which the compound has the formula
Figure imgf000648_0004
wherein:
R'19 is as defined for R1 in claim 1;
X'30 is as defined for X in claim 1;
Z'1 and Y'2 are independently O, S,
C1-C8 alkylidene. substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y'91 and Y'92 are independently halogen, alkyl or alkoxy.
20. The method of claim 1 in which the compound has the formula
wherein:
Figure imgf000649_0001
Y'20 is as defined for R1 in claim 1;
X'31 is as defined for X in claim 1;
Z'3 is O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl. alkenyl or alkynyl; and
Y'93, Y'94 and Y'95 are the same or different and are hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, araIkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 , = X-R3,
-X - R3 ,
Figure imgf000651_0001
Figure imgf000651_0002
or
Figure imgf000651_0003
wherein X, R 3 , R4, R5, Y1, Y2, Y3 and
Y4, are as defined in claim 1.
21. The method of claim l in which the compound has the formula
Figure imgf000652_0001
wherein:
R'21 is as defined for R1 in claim 1;
X'32 is as defined for X in claim 1; and
Y'96, Y'97, Y'98 and Y'99 are the same or different and are hydrogen, halogen, alkyl or alkoxy.
22. The method of claim 1 in which the compound has the formula
Figure imgf000652_0002
wherein:
R'22 is as defined for R1 in claim 1; and and Z'4 are independently hydrogen, halogen, hydroxy. alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl.
23. The method of claim 1 in which the compound has the formula
Figure imgf000653_0001
24. The method of claim 1 in which the compound has the formula
Figure imgf000653_0002
25. The method of claim 1 in which the compound has the formula
Figure imgf000653_0003
26. The method of claim 1 in which the compound has the formula
Figure imgf000654_0001
27. The method of claim 1 in which the compound has the formula
Figure imgf000654_0002
28. The method of claim 1 in which the compound has the formula
Figure imgf000654_0003
29. The method of claim 1 in which the compound has the formula
Figure imgf000654_0004
30. The method of claim 1 in which the compound has the formula
Figure imgf000655_0001
31. The method of claim 1 in which the compound has the formula
Figure imgf000655_0002
32. The method of claim 1 in which the compound has the formula
Figure imgf000655_0003
33. The method of claim 1 in which the compound has the formula
Figure imgf000656_0001
34. The method of claim 1 in which the compound has the formula
Figure imgf000656_0002
35. The method of claim 1 in which the compound has the formula
Figure imgf000656_0003
36. The method of claim 1 in which the compound has the formula
Figure imgf000656_0004
37. The method of claim 1 in which the compound has the formula
Figure imgf000657_0001
38. The method of claim 1 in which the compound has the formula
Figure imgf000657_0002
39. The method of claim 1 in which the compound has the formula
Figure imgf000657_0003
40. The method of claim 1 in which the compound has the formula
Figure imgf000657_0004
41. A method of reducing moisture loss from plants which comprises applying to the plant surface an effective amount, sufficient to reduce moisture loss from the plant surface without substantially inhibiting, plant photosynthetic electron transport, of a compound of claim 105.
42. The method of claim 1 wherein the compound is applied to the plant surface in an amount sufficient to reduce moisture loss from the plant surface without causing substantial inhibition of plant photosynthetic light reactions.
43. The method of claim 1 wherein the compound is applied to the plant surface at a condition of substantially no plant water stress.
44. The method of claim 1 wherein the compound is applied to the plant surface at a period prior to the plant reproductive growth phase.
45. The method of claim 1 wherein the compound is applied to the plant surface at a period prior to substantial soil moisture loss.
46. The method of claim 1 wherein the compound is applied to the plant surface at a period during the plant reproductive growth phase.
47. The method of claim 1 wherein the compound is applied to the plant surface at a concentration of from about 0.1 to about 100 pounds of compound per acre.
48. The method of claim 1 wherein the compound is applied to the plant surface at a concentration of from about 0.25 to about 15 pounds of compound per acre.
49. The method of claim 1 wherein the plant is any agronomic or horticultural crop, ornamental or turfgrass.
50. The method of claim 1 wherein the plant is selected from corn, cotton, sweet potatoes, white potatoes, alfalfa, wheat, rye, upland rice, barley, oats, sorghum, dry beans, soy beans, sugar beets, sunflowers, tobacco, tomatoes, canola, deciduous fruit, citrus fruit, tea, coffee, olives, pineapple, cocoa, banana, sugar cane, oil palm, herbaceous bedding plants, woody shrubs, turfgrasses, ornamental plants, evergreens, trees, and flowers.
51. The method of claim 1 wherein the plant is transplanted stock.
52. The method of claim 51 wherein the transplanted stock is selected from tobacco, tomatoes, eggplant, cucumbers, lettuce, strawberries, herbaceous bedding plants, woody shrubs and tree seedlings.
53. A method of increasing crop yield which comprises applying to the crop an effective amount, sufficient to increase crop yield without substantially inhibiting plant photosynthetic electron transport, of a compound having the formula:
R1 - X - R2 wherein: R1 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl) amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000662_0001
Figure imgf000662_0002
or
; or
Figure imgf000662_0003
R1 is a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3
or
Figure imgf000664_0001
Figure imgf000664_0002
Figure imgf000664_0003
X is a covalent s ingle bond or double bond , a substituted or unsubstituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R 3, = X-R3,
-X - R3 ,
Figure imgf000666_0001
Figure imgf000666_0002
or
and
Figure imgf000667_0001
R2 is a substituted or unsubstituted, heterocyclic ring system having at least one nitrogen atom which is selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhalόacyloxy, aroyloxy , alkylsulf onyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, araIkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 , = X-R3,
-X - R3 ,
or
Figure imgf000669_0001
Figure imgf000669_0002
wherein: R3 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido,alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X at R3, as X-R3,
-X - R3
Figure imgf000671_0001
or
Figure imgf000671_0002
or
Figure imgf000672_0001
R3 is a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, araIkylamino, alkoxyalkylphosphinyl, alkoxyalkylphos-phinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, as X, -X as R3, as X-R3,
-X - R3 ,
Figure imgf000674_0001
Figure imgf000674_0002
or
Figure imgf000674_0003
Y1 and Y4 are independently oxygen or sulfur, Y2 and Y3 are independently oxygen, sulfur, amino or a covalent bond; and R4 and R5 are independently hydrogen or substituted or unsubstituted alkyl, polyhaloalkyl, phenyl or benzyl in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarb,onyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulf inyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, aIkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000676_0001
Figure imgf000676_0002
or
Figure imgf000676_0003
54. The method of claim 53 wherein R1 and R3 are independently a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected frcvm a monocyclic aromatic or nonaromatic ring system having the formula
Figure imgf000677_0001
a bicyclic aromatic or nonaromatic ring system having the formula selected from
Figure imgf000677_0002
and
Figure imgf000677_0003
a polycyclic aromatic or nonaromatic ring system having the formula selected from
Figure imgf000677_0004
Figure imgf000678_0001
and a bridged ring system which may be saturated or unsaturated having the formula selected from
Figure imgf000678_0002
Figure imgf000678_0003
and
Figure imgf000679_0001
wherein: A1 represents a ring-forming chain of atoms which together with B1 forms a carbocyclic or heterocyclic ring system containing from 0 to 4 double bonds or from 0 to 2 triple bonds; B1 represents a saturated or unsaturated carbon atom; A1 and A1 independently represent a
A2 ring-forming chain of atoms which together with B2 and B form a carbocyclic or heterocyclic ring system; B2 and B3 are independently a saturated or unsaturated carbon atom or a saturated nitrogen atom;
A 4, A5, A6, and A7 independently represent a ring-forming chain of atoms which together with B4, B5, B6 and B7 form a carbocyclic or heterocyclic ring system; B4, B5, B6 and B7 are independently a saturated or unsaturated carbon atom or a saturated nitrogen atom; A8, A9 and A10 independently represent a ring-forming chain of atoms which together with B8, B9, B10 and B11 form a carbocyclic or heterocyclic ring system; B8, B9 and B10 are independently a saturated or unsaturated carbon atom or a saturated nitrogen atom; B11 represents a saturated or unsaturated carbon atom, nitrogen atom or phosphorous atom; A11, A12 and A13 independently 11 12 13 represent of atoms which together with B12 and B13 form a carbocyclic or heterocyclic ring system; B12 and B13 are independently a saturated carbon atom or a nitrogen atom; and
Z is the same or different and is one or more of hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulf inyl, haloalkylsulfonyl , haloalknnyloxy , haloalkynyloxy, ha loa lkynylthio , haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, halo-acylamino,- alkoxycarbonyloxy,- arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X a R3, = X-R3,
-X - R3 ,
Figure imgf000682_0001
Figure imgf000682_0002
or
Figure imgf000682_0003
wherein R3, R4 , R5, Y1, Y2, Y3, Y4 and
X are as defined in claim 42.
55. The method of claim 53 in which the compound has the formula
Figure imgf000682_0004
wherein:
R'1 is the same or different and is one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, seruicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3, -X - R3 ,
Figure imgf000685_0001
or
Figure imgf000685_0002
:
X'1 is O, S, SO, SO2, NH, CH2, CO, a single covalent bond, CH2O, CH2S, -CH(CH2)O,
-CH(CN)O-, -CH=NO-, -C(CH3)=NO-, -CH2CH2O-,
-CH2CH2-, -C≡C-, -CH2SO-, -CH2SO -,
-OCH2CH2O-, -CH(alkyl)- or -CONH-; and
Y'1 and Y'2 are independently halogen, alkyl or alkoxy; wherein X, R3, R4, R5, Y1, Y2, Y3 and Y4 are as defined in claim 42,
56. The method of claim 53 in which the compound has the formula
wherein:
Figure imgf000685_0003
R'2 and R'3 are the same or different and R'2 is one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, trialkylsilyloxy, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000687_0001
Figure imgf000687_0002
or
Figure imgf000687_0003
X'2 is O, S, SO, SO2, NH, CH2, CO, a single covalent bond, -CH(CH2)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-, -CH2CH2O-, -C≡C-, -CH2SO- or -CH2SO2-; and Y'3 is halogen; wherein X, R3, R4, R5, Y1, Y2, Y3 and Y4 are as defined in claim 42,
57. The method of claim 53 in which the compound has the formula.
Figure imgf000688_0001
wherein: R'4, R'5 and R'6 are the same or different and R'4 is one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothrocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulponyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, araIkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000690_0001
or
; and
Figure imgf000690_0002
X' is O, S, SO, SO2, NH, CH2, CO, a single covalent bond, -CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-, -CH2CH2O-, -C≡C-, -CH2SO-, -CH2SO2-, -OCH2CH2O-, -CH(alkyl)- or -CONH-:: wherein X, R3, R4, R5, Y1, Y2, Y3 and Y4 are as defined in claim 42.
58. The method of claim 53 in which the compound has the f ormula
Figure imgf000691_0001
wherein:
Y'4, Y'5, Y' 6, Y'7 and Y'8 are the same or different and are hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
or
Figure imgf000693_0001
Figure imgf000693_0002
Y'9, Y'10, Y'11 and Y'12 are the same or different and are hydrogen, halogen, alkyl, polyhaloalkyl, cyano or aryl; m' and n' are the same or different and are a value of from 0 to 5;
X'4 is O, S, SO, SO2, NH, CH2, CO, a single covalent bond, -CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-, -CH2CH2O-, -C≡C-, -CH2SO-, -CH2SO2-, -OCH2CH2O-, -CH(alkyl)- or -CONH-; and
Y'13 and Y'14 are the same or different and are halogen, alkyl or alkoxy; wher in X, R3, R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 42.
59. The method of claim 53 in which the compound has the formula
Figure imgf000694_0001
wherein: Y'4, Y'5, Y'6, Y'7 and Y'8 are the same or different and are hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbo-nyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
or
Figure imgf000696_0001
Figure imgf000696_0002
Figure imgf000696_0003
Y'9 and Y'10 are the same or different and are hydrogen, halogen, alkyl, polyhaloalkyl, cyano or aryl; m' and n' are the same or different and are a value of from 0 to 5; X'5 is the same or different and is O, S, SO, SO2, NH, CH2, CO, a single covalent bond, -CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-, -CH2CH2O- -C≡C-, -CH2SO-, -CH2SO2-, -OCH2CH2O-, -CH(alkyl)- or -CONH-;
Y'15 is O or S;
Y'91 and Y'92 are independently halogen; and
X'6 is O or S; wherein X, R3, R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 42.
60. The method of claim 53 in which the compound has the formula
Figure imgf000697_0001
wherein:
Y'4, Y'5, Y'6, Y'7 and Y'8 are the same as different and are hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio. polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloaryloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000699_0001
Figure imgf000699_0002
or
Figure imgf000699_0003
, X'7 is the same or different and is O, S,
SO, SO2, NH, CH2, CO, a single covalent bond, -CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-, -CH2CH2O-, -C≡C-, -CH2SO-, -CH2SO2-, -OCH2CH2O-, -CH(alkyl)- or -CONH-; m' is a value of from 0 to 5;
Y'93 and Y'94 are independently halogen;
Y'16 is hydrogen, alkyl, alkylcarbonyl, alkylsulfonyl, or polyhaloalkylsulfonyl; wherein X, R3, R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 42.
61. The method of claim 53 in which the compound has the formula
Figure imgf000700_0001
wherein:
Y'4, Y'5, Y'6, Y'7 and Y'8 are the same or different and are hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000702_0001
Figure imgf000702_0002
or
; a
Figure imgf000702_0003
Y'95 and Y'96 are independently halogen; wherein X, R 3 , R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 42.
62. The method of claim 53 in which the compound has the formula
Figure imgf000703_0001
wherein:
Y'19 and Y'21 are the same or different and Y'19 is one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylammocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts formamido, alkyl, alkoxy, polyhaloalkyl, polylaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3
Figure imgf000705_0001
Figure imgf000705_0002
or
Figure imgf000705_0003
A' is as defined for R1 in claim 42; X'10 is as defined for X in claim 42; and
Y'20 is halogen, cyano, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, or polyhaloalkylsulfonyloxy; wherein X, R3, R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 42,
63. The method of claim 53 in which the compound has the formula
Figure imgf000705_0004
wherein:
R'12 is as defined for R1 in claim 42;
Y'22 is halogen, cyano, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, or polyhaloalkylsulfonyloxy; and
Y'23 is hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamir.o, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino , alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diaIkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 , = X-R3,
-X - R3 ,
Figure imgf000708_0001
Figure imgf000708_0002
or
Figure imgf000708_0003
wherein X, R3, R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 42.
64. The method of claim 53 in which the compound has the formula
Figure imgf000708_0004
wherein:
A'1 is as defined for R2 in claim 42; and and Y'32 are the same or different and are halogen, alkyl or alkoxy,
65. The method of claim 53 in which the compound has the formula
Figure imgf000709_0001
wherein:
A'2 is as defined for R1 in claim 42;
X'12 is as defined for X in claim 42; and
Y'33 and Y'34 are the same or different and are halogen, alkyl or alkoxy.
66. The method of claim 53 in which the compound has the formula selected from
Figure imgf000709_0002
Figure imgf000709_0003
Figure imgf000709_0004
Figure imgf000709_0005
Figure imgf000710_0001
wherein: Y'41, Y'42, Y'43, Y'44, Y'45, Y'46, Y'47, Y'48, Y'49, Y'50, Y'51, Y"48, Y'52, Y'53, Y'54, Y'55, Y'56,
Y'57, Y"59, Y'58, Y'59, Y'60, Y'61, and
Y'62 are the same or different and Y'41, Y'45,
Y'48, Y'52, Y'56, and Y'59 are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino. oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy. alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 , = X-R3,
-X - R3 ,
Figure imgf000712_0001
Figure imgf000712_0002
or
Figure imgf000712_0003
A'4, A'5, A'6, A'7, A'8 and A'9 are as defined for R1 in claim 42; and
X'14, X'15, X'16, X'17, X'18 and
X'19 are the same or different and are O, S, SO,
SO2, NH, CH2, CO, a single covalent bond,
-CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-,
-CH2CH2O-, -C≡C-, -CH2SO-, -CH2SO2-,
-OCH2CH2O-, -CH(alkyl)- or -CONH-; wherein X, R3, R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 42.
67. The method of claim 53 in which the compound has the formula
Figure imgf000712_0004
wherein:
A'10 is as defined for R1 in claim 42;
X'20 is as defined for X in claim 42;
A'11 is a substituted or unsubstituted, 5-membered heterocyclic ring system having at least one nitrogen atom in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicar.bazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 , = X-R3,
-X - R3 ,
Figure imgf000715_0001
Figure imgf000715_0002
or
Figure imgf000715_0003
Y'63 and Y'64 are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino , alkoxycarbonyloxy, arylsulf onylamino , aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino. aryl (alkyl) amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3
Figure imgf000717_0001
Figure imgf000717_0002
or
Figure imgf000717_0003
wherein X, R3, R4, R5, Y1, Y2, Y3 and Y4 are as defined in claim 42.
68. The method of claim 53 in which the compound has the formula selected from
Figure imgf000717_0005
Figure imgf000717_0004
Figure imgf000717_0006
Figure imgf000718_0001
wherein: Y'65, Y'66, Y'67, Y'68, Y'69,
Y'70, Y'71, Y'72, Y'73, Y'74, Y'75, Y'76, Y'77, Y'78, Y'79, Y'80 and Y'81 are the same or different and Y'67, Y'70,
Y ' 73 , Y ' 76 and Y ' 79 are one or more hydrogen. halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylammocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio. polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoaIkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, diall'.ylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000720_0001
Figure imgf000720_0002
or
Figure imgf000720_0003
r' is a value of 0 or 1;
A'12, A'13, A'14' A'15, A'16 and
A'17 are as defined for R1 in claim 42; and
X'21, X'22, X'23, X'24, X'25 and
X'26 are as defined for X in claim 42; wherein X, R3, R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 42,
69. The method of claim 53 in which the compound has the formula
Figure imgf000721_0001
wherein:
Y'82, Y'83, Y'84, Y'85 and R'17 are the same or different and are hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonylcxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino. oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy. dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000723_0001
Figure imgf000723_0002
or
; and
Figure imgf000723_0003
X'27 is as defined for X in claim 42; wherein X, R3, R4, R5, Y1, Y2, Y3 and
Y 4 are as defined in claim 42.
70. The method of claim 53 in which the compound has the formula selected from
Figure imgf000723_0004
wherein:
R'18 and Y'90 are the same or different and R'18 is one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminccarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 , = X-R3,
-X - R3 ,
Figure imgf000725_0001
or
Figure imgf000726_0001
A'18 is as defined for R1 in claim 42; and
X'29 is as defined for X in claim 42; wherein X, R3, R4, R5, Y1, Y2, Y3 and
Y4 are as defined in claim 42.
71. The method of claim 53 in which the compound has the formula
Figure imgf000726_0002
wherein:
R'19 is as defined for R1 in claim 1;
X'30 is as defined for X in claim 1;
Z'1 and Z'2 are independently O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y'91 and Y'92 are independently halogen, alkyl or alkoxy.
72. The method of claim 53 in which the compound has the formula
Figure imgf000726_0003
wherein:
R'20 is as defined for R1 in claim 1;
X'31 is as defined for X in claim 1;
Z'3 is O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or
NR''' wherein R''' is alyl, aryl, aralkyl, alkenyl or alkynyl; and
Y' 93, Y'94 and Y'95 are the same or different and are hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylammocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbon; loxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyaraino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000729_0001
Figure imgf000729_0002
or
Figure imgf000729_0003
wherein X, R 3, R4 , R5, Y1, Y2, Y3 and
Y4 are as defined in claim 1.
73. The method of claim 53 in which the compound has the formula
Figure imgf000729_0004
wherein:
R'21 is as defined for R1 in claim 1;
X'32 is as defined for X in claim 1; and Y, 96, Y' 97, Y' 98 and Y' 99 are the same or different and are hydrogen, halogen, alkyl or alkoxy.
74. The method of claim 53 in which the compound has the formula
Figure imgf000730_0001
wherein: R'22 is as defined for R1 in claim 1; and
X'33 and Z'4 are independently hydrogen, halogen, hydroxy, alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl.
75. The method of claim 53 in which the compound has the formula
76. The method of claim 53 in which the compound has the formula
Figure imgf000730_0003
77. The method of claim 53 in which the compound has the formula
Figure imgf000731_0001
78. The method of claim 53 in which the compound has the formula
Figure imgf000731_0002
79. The method of claim 53 in which the compound has the formula
Figure imgf000731_0003
80. The method of claim 53 in which the compound has the formula
Figure imgf000731_0004
81. The method of claim 53 in which the compound has the formula
Figure imgf000732_0001
82. The method of claim 53 in which the compound has the formula
Figure imgf000732_0002
83. The method of claim 53 in which the compound has the formula
Figure imgf000732_0003
84. The method of claim 53 in which the compound has the formula
Figure imgf000733_0001
85. The method of claim 53 in which the compound has the formula
Figure imgf000733_0002
86. The method of claim 53 in which the compound has the formula
Figure imgf000733_0003
87. The method of claim 53 in which the compound has the formula
Figure imgf000733_0004
88. The method of claim 53 in which the compound has the formula
Figure imgf000734_0001
89. The method of claim 53 in which the compound has the formula
Figure imgf000734_0002
90. The method of claim 53 in which the compound has the formula
Figure imgf000734_0003
91. The method of claim 53 in which the compound has the formula
Figure imgf000734_0004
92. The method of claim 53 in which the compound has the formula
Figure imgf000734_0005
93. A method of increasing crop yield which comprises applying to the crop an effective amount, sufficient to increase crop yield without substantially inhibiting plant photosynthetic electron transport, of a compound of claim 105.
94. The method of claim 53 wherein the compound is applied to the crop in an amount sufficient to increase crop yield without causing substantial inhibition of plant photosynthetic light reactions.
95. The method of claim 53 wherein the compound is applied to the crop at a condition of substantially no plant water stress.
96. The method of claim 53 wherein the compound is applied to the crop at a period prior to the plant reproductive growth phase.
97. The method of claim 53 wherein the compound is applied to the crop at a period prior to substantial soil moisture loss.
98. The method of claim 53 wherein the compound is applied to the crop at a period during the plant reproductive growth phase.
99. The method of claim 53 wherein the compound is applied to the crop at a concentration of from about 0.1 to about 100 pounds of compound per acre.
100. The method of claim 53 wherein the compound is applied to the crop at a concentration of from about 0.25 to about 15 pounds of compound per acre.
101. The method of claim 53 wherein the crop is any agronomic or horticultural crop.
102. The method of claim 53 wherein the crop is selected from corn, cotton, sweet potatoes, white potatoes, alfalfa, wheat, rye, upland rice, barley, oats, sorghum, dry beans, soybeans, sugar beets, sunflowers, tobacco, tomatoes, canola, deciduous fruit, citrus fruit, tea. coffee, olives, pineapple, cocoa, banana, sugar cane and oil palm.
103. The method of claim 53 wherein the crop is transplanted stock.
104. The method of claim 103 wherein the transplanted stock is selected from tobacco, tomatoes, eggplant, cucumbers, lettuce, strawberries, herbaceous bedding plants, woody shrubs and tree seedlings.
105. A compound having the formula selected from the following:
Figure imgf000737_0001
wherein:
R24 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X10 represents O, S, SO, SO2, NH,
-CH2O-, -CH2S-, -CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-, -CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-, -CH2SO2-, -OCH2CH2O-, -CH(alkyl)- or -CONH-; j is a value of 0 or 1; a is a value of from 2 to 4 inclusive; and
Y19 is the same or different and represents halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl provided that (i) at least two ring position pairs selected from 2 and 4, 2 and 6, 2 and 3, and 3 and 4 are substituted with the same or different halogen; (ii) when ring positions 2,4 and 6 are substituted with chlorine and j is a value of 0 and X10 is
SO2, then R24 is not unsubstituted phenyl; and
(iii) when ring positions 2,3 and 5 are substituted with chlorine and j is a value of 1 and X is S, then R24 is not unsubstituted phenyl;
Figure imgf000738_0001
wherein:
R25 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X11 represents O, S, SO, SO2, NH, CH2, a single covalent bond, -CH2O-, -CH2S-, -CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-, -CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-, -CH2SO2-, -OCH2CH2O-, -CH(alkyl)- or -CONH-; b is a value of 2 to 3; and
Y20 is the same or different and represents halogen, alkyl, cyano, polyhaloalkyl, polyhaloalkoxy, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl provided that at least two of Y20 are halogen;
Figure imgf000738_0002
wherein:
R26 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X12 represents O, S, SO, SO2, NH, 2
CH2, a single covalent bond, -CH2O-, -CH2S-, -CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO2-, -OCH2CH20-, -CH(alkyl)- or -CONH-;
Y21 and Y22 are independently the same or different halogen; and
Y23 represents hydrogen, halogen, alkyl, polyhaloalkyl, alkoxy, polyhaloalkoxy, cyano, alkylthio. alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl;
Figure imgf000739_0001
wherein:
R27 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X13 represents O, S, SO, SO2, NH,
CH2, a single covalent bond, -CH2O-, -CH3S-, -CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO2-, -OCH2CH2O-, -CH(alkyl)- or -CONH-;
Y24 represents halogen; and Y25 and Y26 independently represent hydrogen, halogen, alkyl, polyhaloalkyl, alkoxy, polyhaloalkoxy, cyano, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl provided that at least one of Y25 and Y26 is halogen and further prov .ided that when Y24, Y25 and Y26 are chloro and X13 is O, then R27 is not unsubstituted phenyl;
Figure imgf000740_0001
wherein:
R28 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X14 represents O, S, SO, SO2, NH,
CH2, a single covalent bond, -CH2O-, -CH2S-,
-CH(CH2)O-, -CH(CN)O-, -CH=NO-, -C(CH2)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO2 , -OCH2CH2O-, -CH(alkyl)- or -CONH-;
Y27 and Y28 are independently halogen: and
Y29 represents hydrogen, halogen, alkyl, polyhaloalkyl, alkoxy, polyhaloalkoxy, cyano, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl;
Figure imgf000740_0002
wherein:
R29 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X15 represents O, S, SO, SO2, NH,
CH2, a single covalent bond, -CH2O-, -CH2S-,
-CH(CH2)O-, -CH(CN)O-, -CH=NO-, -C(CH2)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO2-, -OCH2CH2O-, -CH(alkyl)- or -CONH-; and
Y30, Y31 and Y32 independently represent hydrogen, halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl provided that at least two of
Y30, Y31 and Y32 are halogen;
Figure imgf000741_0001
wherein:
R30 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X16 represents O, S, SO, SO2, NH,
CH2, a single covalent bond, -CH2O-, -CH2S-,
-CH(CH2)O-, -CH(CN)O-, -CH=NO-, -C(CH2)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO2-, -OCH2CH2O-, -CH(alkyl)- or -CONH-; and
Y33, Y34 and Y35 independently represent hydrogen, halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl or polyhaloalkylsulfonyl provided that (i) at least two of Y 33, Y34 and Y35 are halogen, (ii) when
Y34 and Y35 are both chloro and X16 is O, then
R30 is not unsubstituted phenyl, and (iii) when Y33 and Y34 are both chloro and X16 is O, then
R30 is not unsubstituted phenyl or 4-methoxyphenyl;
Figure imgf000742_0001
wherein: d is a value of from 0 to 4 inclusive; e is a value of 1 or 2 provided that d + e are not greater than 5;
R31 is the same or different and represents unsubstituted or substituted aryl provided that when R31 is 2- or 4-aryl then d is not O; aralkyl provided that when R31 is 4-aralkyl then d is not O; alkoxy, cycloalkoxy, aryloxy, aralkoxy provided that when R31 is 4-aralkoxy then d is not O; arylaryloxy, aralkoxyaralkyl, arylaralkoxy, aryloxyaralkyl, aryloxyalkyl, aryloxyaryloxy, aralkoxyaralkoxy, aryloxyalkoxy, alkylthio, alkenylthio, arylthio, aralkylthio, arylthioaralkyl, arylsulfonylarylsulfonyl, alkylamino, dialkylamino, acyloxy, aroyloxy, alkoxycarbonyloxy, phenylazo provided that X17 is O or S: naphthylazo, or -OCH2O- or -OCH2CH2O- which join adjacent carbon atoms to form a five- or six-membered ring;
Y36 is the same or different and represents halogen, alkyl, alkenyl, alkynyl, -CH=CHCH=CH- which joins adjacent carbon atoms to form a six-membered ring, -(CH2)4, nitro, cyano, haloalkyl, or polyhaloalkyl:
X17 represents O, S, NH, CH2, -CH2O-,
-CH2S- or -OCH2CH2O-;
Y37 represents halogen; and
Y38 represents halogen, alkoxy, alkylthio, alkylsulfonyl, polyhaloalkoxy, polyhaloalkyl, cyano, nitro or unsubstituted or substituted arylthio, aryloxy or arylsulfonyl;
Figure imgf000743_0001
wherein: f is a value of from 0 to 5;
R32 is the same or different and represents halogen, alkyl, alkenyl, alkynyl, polyhaloalkyl, cyano, nitro, alkylamino, dialkylamino, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, acyl, CO2(alkyl), CONH(alkyl), CON(alkyl)2, SO2N(alkyl) , alkylcarbonyloxy, alkoxycarbonyloxy, or unsubstituted or substituted aryloxy, arylthio, arylsulfonyl or aroyl; X18 represents O, S, CH2, a single covalent bond or -C≡C-;
Y39 represents halogen, polyhaloalkoxy, polyhaloalkyl, cyano, alkylsulfonyl, alkylsulfonyloxy, polyhaloalkylsulfonyl or polyhaloalkylsulfonyloxy; and
Y40 represents haloalkyl, polyhaloalkyl, alkoxy provided that X18 is not S or a single covalent bond; polyhaloalkoxy, cyano, alkylthio provided that X18 is not O or a single covalent bond; alkylsulfonyl, nitro, dialkoxyphosphinyl or trialkylammonium;
Figure imgf000744_0001
wherein:
Y41 is the same or different and represents halogen;
Y42 is the same or different and represents halogen, alkoxy, alkylthio or polyhaloalkoxy; and X19 represents O, -S-S-, -P(=O)(O-alkyl)-, -P(alkyl)-, -P(O-alkyl)-, sulfinyl, sulfonyl, thiosulfinyl, a single covalent bond, carbonyl, aminocarbonylamino, aminooxalyl- amino, aminocarbonylalkylenecarbonylamino, aminoalkyleneamino, unsubstituted or substituted oxyaryloxy provided that 1,3-arylenebis(oxy) is substituted with at least one substitutent; oxyarylalkylaryloxy, oxyarylthioaryloxy, oxyarylsulfonylaryloxy and oxyarylaryloxy;
Figure imgf000745_0001
wherein:
Y52 and Y53 are independently halogen; g is a value of from 0 to 5 inclusive;
R33 is the same or different and represents halogen, alkyl, alkenyl, alkynyl, polyhaloalkyl, cyano, nitro, amino, alkylamino, dialkylamino, alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl. polyhaloalkylsulfonyl. alkoxycarbonyl, alkylaminocarbonyl, aminocarbonyl, dialkylaminocarbonyl, dialkylaminosulfonyl, alkylaminosulfonyl, aminosulfonyl, alkylcarbonyl, dialkoxyalkyl, alkylcarbonyloxy, alkylcarbonylalkylamino, -CH=CHCH=CH- which joins adjacent carbon atoms to form a six-membered ring, or unsubstituted or substituted aryl, aralkyl, aryloxy. arylthio. arylsulfonyl or aralkoxy; and
X20 represents -CH(alkyl)O-, -C(alkyl)2O-, -OCH2-. -CH2O-, -CH2-, -C(halogen)2, -OCH2O-, -OCH2CH2O- or -C=C-provided that g is a value of at least 1;
-OCH(alkyl)-, -OC(alkyl)2, -OCH(aIkyl)O-,
-OC(alkyl)2O-, -OCH(alkyl)CH2O-,
-OCH(alkyl)CH(alkyl)O-, -CH(alkyl)CH(alkyl)-,
-CH(alkyl)-, -C(alkyl)2-, -CH2CH2O-,
-OCH2CH2-, -CH(alkyl)CH2O-, -CH2CH2-,
-CH(CN)O-, -C(alkyl)(CN)O-, -CH(polyhaloalkyl)O-,
-C(CN)=NO-, -C(NH alkyl)=NO-, -C[N(alkyl)2]=NO-,
-C(S-alkyl)=NO-, -C(O-alkyl)=NO-, -SC(=O)O-,
-NHC(=O)O-, -N(alkyl)C(-O)O-, SO, SO2,
-CH2S(O)h-, -CH(alkyl)S(O)h-, -S(O)hCH2-,
-OC(=S)S-, -C(=O)S-, -C(=S)-S-, -NH(alkyl)C(=O)S-, -O(C=O)S-, -N(R34)-, -SO2NH-, -SO2N(alkyl)-, -CONH-, -CON(alkyl)-, -SC(=O)N(alkyl)-, -S-C(=O)NH-, -NHSO2NH-, -N(alkyl)SO2N(alkyl)-, -N(alkyl)SO2NH-, -NHSO2N(alkyl)-, -C(O-alkyl)=N-, -C(S-alkyl)=N-, -CH(halogen)-, -C(alkyl) (halogen), -CH(CN)-, -C(alkyl) (CN)-, -NH(alkyl)NH-, -NH-N(alkyl)-; -NH-NH- or -N=N- provided that R33 is not nitro; -C(=O)-, -C(=O)C(=O)-, -CH(O-alkyl)-, -CH2C(=O)-, -C(-O)CH2, -CH(alkyl)C(=O)-, -C(=O)CH(alkyl)-, -CH=CH-, -C(alkyl)=CH-, -CH=C(alkyl)-, -C(alkyl)=C(alkyl)-, -C(=O)CH-CH-, -P(Y43)(Y44-alkyl)-, unsubstituted or substituted -P(Y43) (Y44-aryl) or arylene,
-Si(halogen)2-, -Si(alkyl)2, -OC(=O)N(alkyl)-, -OCH2C(=O)N(alkyl)-, -N(alkyl)CON(alkyl)-; -OC(=O)NH-, -NHCONH-, -SO2NHC(=O)NH-, or -NHC(=S)NH provided that g is a value of at least 1;
Figure imgf000747_0002
wherein h is a value of from 0 to 2 inclusive, R34 represents acyl, alkylsulfonyl, polyhaloalkyl, polyhaloacyl, polyhaloalkylsulfonyl or unsubstituted or substituted aroyl or arylsulfonyl and Y43 and
Y44 are independently O or S;
Figure imgf000747_0001
wherein:
R35 represents an unsubstituted or substituted heterocyclic ring system selected from isoxazole. isothiazole, pyrazole, imidazole, 1.2.4-triazole, 1,2,4-oxadiazole. 1,3,4-oxadiazole, 1,2,4,-thiadiazole, 1,3,4-thiadiazole, oxazole, thiazole, benzopyrazole. benzimidazole, benzoxazole, benzothiazole, indole, pyrrole, furan, thiophene, benzofuran, benzothiophene, pyridine, pyrimidine, pyridazine, pyrazine, 1,3, 5-triazine, 1,2,4-triazine, quinoline, isoquinoline, quinazoline, phthalazine, benzopyridazine, benzopyrazine, carbazole, dibenzofuran, dibenzothiophene, benzoxazine, phthalimide, benzopyran, dibenzopyridine, pyridopyridine, pyrazolopyrimidine, tetrahydropyrimidinedione, coumarin, piperidine, morpholine, tetrahydrofuran, tetrahydrothiophene, pyrrolidine, thiomorpholine, piperidine-2-one, piperidine-2, 6-dione, 2, 5-pyrrolidinedione, 3-morpholinone, 2-oxohexamethyleneimine, 2-oxotetramethyleneimine, 1-pyrazoline, 2-pyrazoline, pyrazolidine, 2-imidazolidinone, 2-imidazolidinethione, 2,4-imidazolidinedione, 1, 2-oxathiolane, 1,3-oxathiolane, 1,3-oxathiane, 1,4-oxathiane, 2(1H)-pyrazinone, 2H-pyran-2-one, 4H-pyran-4-one, 2H-pyran-2-thione, 4H-pyran-4-thione, tetrahydropyran, tetrahydrothiopyran, 7-oxabicyclo[2.2.1]heptane,
7-azabicyclo[2.2.1]heptane, oxetane, coumarin, 1,3-dioxane, 1.4-dioxane or 1, 3-dioxolane;
X represents O, S or NH provided that when X21 is NH then R35 is not pyridine, and when X21 is s then R35 is not unsubstituted benzothiazole; and
Y45 and Y46 are independently halogen;
Figure imgf000748_0001
or
Figure imgf000749_0001
wherein:
R37 and R38 independently represent halogen, nitro, cyano, polyhaloalkyl, polyhaloalkoxy, alkylsulfonyl, polyhaloalkylsulfonyl, acyl, alkoxycarbonyl, polyhaloalkylsulfonyl or R39-X22- Provided that only one of R37 and R38 may be R39-X22- at any one time;
R39 reprresents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl; X represents O, S, SO, SO2, CH2, a single covalent bond, -CH2O-, -CH2S-,
-CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO2-, -OCH2CH2O-, -CH(alkyl)- or -CONH-;
Y47 represents halogen; and
B14 represents O, S, NH or NR40 wherein
R40 represents alkyl, alkylsulfonyl. alkenyl, alkynyl, alkoxycarbonyl; unsubstituted or substituted aryl, aralkyl, aryloxy, arylamino, aroyl or arylsulfonyl; provided that (i) when B14 is R39-
Figure imgf000750_0003
' R39-alkyl-
Figure imgf000750_0005
R39-C(=O)-
Figure imgf000750_0009
, R39-SO2
Figure imgf000750_0004
, R39-O-
Figure imgf000750_0014
or R39-NH-
Figure imgf000750_0010
, then both R37 and R38 are other than R39-X22-; (ii) when B14 is other than R39-
Figure imgf000750_0011
, R39-alkyl-
Figure imgf000750_0013
,
R39-C(=O)-
Figure imgf000750_0006
, R39-SO2
Figure imgf000750_0008
, R39-O-
Figure imgf000750_0012
or
R39-NH-
Figure imgf000750_0007
, then one of R37 and R38 is
R39-X22-: and (iii) when R38 and Y47 are both chlorine and X22 is a single covalent bond in formula (xiii), then R39 is not unsubstituted phenyl;
Figure imgf000750_0001
Figure imgf000750_0002
wherein:
R41 and R42 independently represent halogen or R43-X23- provided
R41 and R42 may be R43-X23- at any one time;
R43 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X23 represents O, S, SO, SO2, CH2, a single covalent bond, -CH2O-, CH2S-,
-CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH2)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-, -CH2SO2-, -OCH2CH2O-, -CH(alkyl)- or -CONH-; and
B15 represents O, S, NH or N R44 wherein
R44 represents alkyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkenyl, alkynyl, alkoxycarbonyl; unsubstituted or substituted aryl, aralkyl, aryloxy, arylamino, aroyl or arylsulfonyl; provided that when B15 is R43-
Figure imgf000751_0003
, R43-alkyl-
Figure imgf000751_0006
, R43-C(=O)-
Figure imgf000751_0005
R43-SO2
Figure imgf000751_0004
,
R43-O-
Figure imgf000751_0014
or R43-NH-
Figure imgf000751_0007
, then both R41 and R42 are other than R43-R23-; and further provided that when B15 is other than R43-
Figure imgf000751_0008
, R43-alkyl-
Figure imgf000751_0009
, R43-C(=O)-
Figure imgf000751_0011
, R43-SO2
Figure imgf000751_0012
, R43-O-
Figure imgf000751_0010
or
R43-NH-
Figure imgf000751_0013
, then one of R41 and R42 is
R43-X23-;
Figure imgf000751_0001
Figure imgf000751_0002
wherein:
R45, R46, R47, and R48 independently represent hydrogen, halogen, nitro, cyano, polyhaloalkyl, polyhaloalkoxy, alkylsulfonyl, polyhaloalkylsulfonyl, acyl, alkylthio, alkyl, alkoxy, alkylsulfinyl or R49- R24- provided that one of R 45, R46, R47, and R48 is
R49-X24- and further provided that R45, R46, R47, and R48 include no more than two of hydrogen, alkyl or alkoxy at any one time; R49 represents unsubstituted or substituted phenyl, 1- or 2-naphthyl or heteroaryl;
X24 represents O, S, SO, SO2, CH2, a single covalent bond, -CH2O-, -CH2S-,
-CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO -, -OCH2CH2O-, -CH(alkyl)- or -CONH-;
R48 represents halogen; and B16 represents O, S or NH;
Figure imgf000752_0001
wherein:
R50 represents an unsubstituted or substituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring syecem, and a bridged ring system which may be saturated or unsaturated;
B17 represents -CH=N-, -N=CH-, -CH=CH-,
-CO-, -SO2-, -CH2CO-, -COCH2-, -CONH-, -NHCO-, -SO2NH-, -NHSO2-, -SO2N(alkyl)-, -N(alkyl)SO2-, -OSO2-, -CS-, -
Figure imgf000752_0002
, -NH-, -N(alkyl)-, -OCH2-, -SCH2-, -NHCH2-, -N(alkyl)CH2-, -SCO-, -OCH2-, -OCO-, -CH2-,
-CH2CH2- or -SCH2CO-; provided that when B17 is -CO- and R50 is phenyl, then the phenyl is substituted; and
Y54 and Y55 are independently halogen:
Figure imgf000753_0001
wherein:
R51 represents or unsubstituted or substituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated:
R18 represents -CH=N-, -N=CH-, -CH=CH-, -CO-, -SO2-, -CH2CO-, -COCH2-, -CONH-, -NHCO-, -SO2NH-, -NHSO2-, -SO2N(alkyl)-, -N(alkyl)SO2-, -OSO2-, -CS-, -
Figure imgf000753_0002
, -NH-,-N(alkyl)-, -OCH2, -SCH2-, -NHCH2-, -N(alkyl)CH2, -S-CO-, -OCH2-, -OCO-, -CH2-, -CH2CH2- or -SCH2CO-; B19 represents -CH2- or -CH(alkyl)-; and i is a value of 0 or 1; and Y56 and Y57 are independently halogen;
Figure imgf000754_0001
wherein:
B20 represents -CH2C(CH3)2SCH2-,
-CH2CH=C(CH3)OCH2-, -CH2CH2SCH2CH(CH3)-,
-CH2CH2SCH2CH2-, -CH2SCH2CO-,
-COCH2C(CH3)2CH2CO-,
-COCH2CH(C6H5)CH2CO-,
-CONH(C6H5)CH2CH2CO-, -COC(CH3)2NHCO-,
-CH2CH2N(C6H5)CH2CH2-,
-CH2N(C6H5)CH2CH2-,
-CH2CH2CH(C6H5)CH2CH2-, -CO(CH2)3CO-,
-CO(CH2)2CO-, -COCH2CH(CH3)CH2CO-,
-COCH(CH3)CH2CO-, -COC(CH3)2CH2CO-,
-COC(CH3)2C(CH3)2CO-, -CO(CH2)4CO-,
-CO(CH2)5CO-, -CO(CH2)5CH2-,
-CO(CH2)4CH2-, -CO(CH2)3CH2-,
-CO(CH2)2CH2-, -COCH2SCH2CO-,
-COCH2N(R52)CH2CO-, -COCH2OCH2CO-,
-COCH2SCS-, -COCH=CH-N=CH-,
-CH2CH(C6H5)CH2-N=CH-, or -CO2-CH2CH2-; R52 represents hydrogen, alkenyl: unsubstituted or substituted aryl or alkaryl; and
Y58 and Y59 are independently halogen;
Figure imgf000755_0001
wherein:
R53 represents unsubstituted or substituted cycloalkenyl, cycloalkadienyl, cycloalkatrienyl, bicycloalkyl, bicycloalkenyl, bicycloalkadienyl, tricycloalkyl, tricycloalkenyl or tricycloalkadienyl in which the permissible substituents are the same or different and are one or more alkyl, halogen, haloalkyl, polyhaloalkyl, alkoxy, alkylthio, alkylsulfonyl. polyhaloalkoxy, nitro, cyano, acyl, aroyl, aryl, alkoxycarbonyl, alkoxycarbonyloxy, acyloxy, oxo, or -CH=CHCH=CH- or
-CH=CHCH2- which join adjacent carbon atoms tO form a six-or five membered ring;
Y60 and Y61 are independently haloger; and X25 represents O, S, NH, CH2, -CH2O- or a single covalent bond;;
Figure imgf000756_0001
wherein:
Y62 is the same or different and is one or more hydrogen, halogen, alkyl, aryl, aralkyl, alkenyl, alkynyl, polyhaloalkyl, NH , NH(alkγl),
N(alkyl) , alkoxy, polyhaloalkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, aralkoxy, CO alkyl,
CONH(alkyl), CONH , CON(alkyl) ,
SO N(alkyl) , SO NH(alkyl), SO NH , acyl,
CO(O-alkyl) , acyloxy, acyl-CON(alkyl), or
2,3-(-CH=CHCH=CH-), 3,4-(-CH=CHCH=CH-),
2,3-(CH2)4- or 3,4-(CH2)4- which join the adjacent carbon atoms to form an unsubstituted or substituted six-membered ring;
X26 represents O, S, SO, SO2, CH2, a single covalent bond, -CH2O-, -CH2S-,
-CH(CH3)O-, -CH(CN)O-, -CH=NO-, -C(CH3)=NO-,
-CH2CH2O-, -CH2CH2-, -C≡C-, -CH2SO-,
-CH2SO2-, -OCH2CH2O-, -OCH2CH2- or
-OCH2-; and
Y50 and Y51 are the same or different and are halogen;
Figure imgf000757_0001
R68 represents unsubstituted or substituted phenyl or 1- or 2-naphthyl;
X27 represents -CH(alkyl)O-, -C(alkyl)2O-, -OCH2-, -C(halogen)2, -OCH2O-,
-OCH2CH2O-, -CH2O-, -C≡C-, -OCH(alkyl)-,
-OC(alkyl) , -OCH(alkyl)O-, -OC(alkyl)2O-,
-OCH(alkyl)CH2O-, -OCH(alkyl)CH(alkyl)O-,
-CH(alkyl)CH(alkyl)-, -CH(alkyl)-, -C(alkyl)2-,
-CH2CH2O-, -OCH2CH2-, -CH(alkyl)CH2O-,
-CH2CH2-, -CH(CN)O-, -C(alkyl)(CN)O-,
-CH(polyhaloalkyl)O-, -C(CN)=NO-, -C(NH2alkyl)=NO-,
-C[N(alkyl)2]=NO-, -C(S-alkyl)=NO-,
-C(O-alkyl)=NO-, -SC(=O)O-, -NHC(=O)O-,
-N(alkyl)C(=O)O-, SO, SO2, -CH2S(O)h-,
-CH(alkyl)S(O)h-, -S(O)hCH2-, -OC(=S)S-,
-C(=O)S-, -C(=S)-S-, -NH(alkyl)C(=O)S-, -O(C=O)S-,
-N(alkyl)-, -N(R34)-,-SO2NH-, -SO2N(alkyl)-,
-CONH-, -CON(alkyl)-, -SC(=O)N(alkyl)-, -S-C(=O)NH-, -NHSO2NH-, -N(alkyl)SO2N(alkyl)-. -N(alkyl)SO2NH-, -NHSO2N(alkyl)-, -C(O-alkyl)=N-, -C(S-alkyl)-N-, -CH(halogen)-, -C(alkyl) (halogen)-, -CH(CN)-, -C(alkyl) (CN)-, -NH(alkyl)NH-, -NH-N(alkyl)-; -NH-NH-, -N=N-, -C(=O)-, -C(=O)C(=O)-, -CH(O-alkyl)-, -CH2C(=O)-, -C(=O)CH2, -CH(alkyl)C(=O)-, -C(=O)CH(alkyl)-, -CH=CH-, -C(alkyl)=CH-, -CH-C(alkyl)-,
-C(alkyl)=C(alkyl)-, -C(=O)CH=CH-,
-P(Y43)(Y44-alkyl)-, unsubstituted or substituted -P(Y43) ( Y44-aryl) or arylene.
-Si(halogen)2-, -Si(alkyl)2, -OC(=O)N(alkyl)-, -OCH2C(=O)N(alkyl)-, -N(alkyl)CON(alkyl)-; -OC(=O)NH-, -NHCONH-, -SO2NHC(=O)NH-, -NHC(=S)NH,
Figure imgf000758_0001
wherein h is a value of from O to 2 inclusive, R34 represents acyl, alkylsulfonyl, polyhaloalkyl, polyhaloacyl, polyhaloalkylsulfonyl or unsubstituted or substituted aroyl or arylsulfonyl and Y43 and
Y44 are independently O or S; Z1 and Z2 are independently O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y67 and Y68 are the same or different and represent hydrogen,halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, aryl, polyhaloalkylsulfonyl, alkylamino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino;
Figure imgf000759_0001
R69 represents unsubstituted or substituted phenyl or 1- or 2-naphthyl;
X28 is NH, CH2 or a covalent bond; Z3 and Z4 are independently O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y69 and Y70 are the same or different and represent hydrogen, halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, aryl, polyhaloalkylsulfonyl, alkylamino, dialkylammo, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino, with the proviso that Y69 and Y70 taken together do not represent either the same halogen or halogen and hydrogen;
Figure imgf000759_0002
R70 represents an unsubstituted or substituted, unsaturated or saturated, aromatic or non-aromatic heterocyclic ring system selected from isoxazole, isothiazole, pyrazole, imidazole, 1,2,4-triazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4,-thiadiazole, 1,3,4-thiadiazole, oxazole, thiazole, benzopyrazole, benzimidazole, benzoxazole, benzothizole, indole, pyrrole, furan, thiophene, benzofuran, benzothiophene, pyridine, pyrimidine, pyridazine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, quinoline, isoquinoline, quinazoline, phthalazine, benzopyridazine, benzopyrazine, carbazole, dibenzofuran, dibenzothiophene, benzoxazine, phthalimide, benzopyran, dibenzopyridine, pyridopyridine, pyrazolopyrimidine, tetrahydropyrimidinedione, piperidine, morpholine, tetrahydrofuran, tetrahydrothiophene, pyrrolidine, thiomorpholine, piperidine-2-one, piperidine-2, 6-dione, 2,5-pyrrolidinedione, 3-morpholinone, 2-oxohexamethyleneimine, 2-oxotetramethyleneimine, 1-pyrazoline, 2-pyrazoline, pyrazolidine, 2-imidazolidinone, 2-imidazolidinethione, 2,4-imidazolidinedione, 1,2-oxathiolane, 1,3-oxathiolane, 1,3-oxathiane, 1,4-oxathiane, 2(1H)-pyrazinone, 2H-pyran-2-one, 4H-pyran-4-one, 2H-pyran-2-thione, 4H-pyran-4-thione, tetrahydropyran, tetrahydrothiopyran, 7-oxabicyclo[2.2.1]heptane,
7-azabicyclo[2.2.1]heptane, oxetane, coumarin, 1,3-dioxane, 1,4-dioxane or 1,3-dioxolane;
X29 represents -CH(alkyl)O-, -C(alkyl)2O-, -OCH2-, -CH2O-, -CH2-, a covalent bond, -C(halogen)2, -OCH2O-, -OCH2CH2O-, -C≡C-, -OCH(alkyl)-, -OC(alkyl)2, -OCH(alkyl)O-, -OC(alkyl)2O-, -OCH(alkyl)CH2O-,
-OCH(alkyl)CH(alkyl)O-, -CH(alkyl)CH(alkyl)-,
-CH(alkyl)-, -C(alkyl)2-, -CH2CH2O-,
-OCH2CH2-, -CH(alkyl)CH2O-, -CH2CH2-,
-CH(CN)O-, -C(alkyl)(CN)O-, -CH(polyhaloalkyl)O-,
-C(CN)=NO-, -C(NH alkyl)=NO-, -C[N(alkyl)2]=NO-,
-C(S-alkyl)=NO-, -C(O-alkyl)=NO-, -SC(=O)O-,
-NHC(=O)O-, -N(alkyl)C(=O)O-, SO, SO2,
-CH2S(O)h-, -CH(alkyl)S(O)h-, -S(O)hCH2-,
-OC(=S)S-, -C(=O)S-, -C(-S)-S-, -NH(alkyl)C(=O)S-,
-O(C=O)S-, -NH-, -N(alkyl)-, -N( R34)-,-SO2NH-,
-SO2N(alkyl)-, -CONH-, -CON(alkyl)-,
-SC(=O)N(alkyl)-, -S-C(=O)NH-, -NHSO2NH-,
-N(alkyl)SO2N(alkyl)-, -N(alkyl)SO2NH-,
-NHSO2N(alkyl)-, -C(O-alkyl)=N-, -C(S-alkyl)=N-,
-CH(halogen)-, -C(alkyl) (halogen)-, -CH(CN)-,
-C(alkyl)(CN)-, -NH(alkyl)NH-, -NH-N(alkyl)-;
-NH-NH-, -N-N-, -C(=O)-, -C(=O)C(=O)-,
-CH(O-alkyl)-, -CH2C(=O)-, -C(=O)CH ,
-CH(alkyl)C(=O)-, -C(=O)CH(alkyl)-, -CH=CH-,
-C(alkyl)=CH-, -CH-C(alkyl)-, -C(alkyl)=C(alkyl)-,
-C(=O)CH=CH-, -P( Y43)(Y44-alkyl)-, unsubstituted or substituted -p( Y43) ( Y44-aryl) or arylene,
-Si(halogen)2-, -Si(alkyl)2, -OC(=O)N(alkyl)-, -OCH2C(=O)N(alkyl)-, -N(alkyl)CON(alkyl)-;
-OC(=O)NH-, -NHCONH-, -SO2NHC(=O)NH-, -NHC(=S)NH-,
Figure imgf000761_0001
wherein h is a value of from 0 to 2 inclusive, R 34 represents acyl, alkylsulfonyl, polyhaloalkyl, polyhaloacyl, polyhaloalkylsulfonyl or unsubstituted or substituted aroyl or arylsulfonyl and Y43 and
Y44 are independently O or S;
Z5 and Z6 are independently O, S,
C 1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y71 and Y72 are the same or different and represent hydrogen, halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, amino, alkylamino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, alkoxycarbonyl, alkylaminocarbonyl, aminocarbonyl, dialkylaminocarbonyl, dialkylaminosulfonyl, alkylaminosulfonyl, aminosulfonyl, dialkoxyalkyl, arylsulfonyl, phosphono or phosphino;
Figure imgf000762_0001
R71 represents unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkadienyl, cycloalkatrienyl, bicycloalkyl, bicycloalkenyl, bicycloalkadienyl, tricycloalkyl, tricycloalkenyl or tricycloalkadienyl;
X30 represents -CH(alkyl)O-, -C(alkyl)2O-, -OCH2-, -CH2O-, -CH2-, a covalent bond, -C(halogen)2, -OCH2O-, -OCH2CH2O-, -C≡C-, -OCH(alkyl)-, -OC(alkyl)2, -OCH(alkyl)O-, -OC(alkyl)2O-, -OCH(alkyl)CH2O-,
-OCH(alkyl)CH(alkyl)O-, -CH(alkyl)CH(alkyl)-,
-CH(alkyl)-, -C(alkyl)2-, -CH2CH2O-,
-OCH2CH2-, -CH(alkyl)CH2O-, -CH2CH2-,
-CH(CN)O-, -C(alkyl)(CN)O-, -CH(polyhaloalkyl)O-,
-C(CN)-NO-, -C(NH alkyl)-NO-, -C[N(alkyl)2]=NO-,
-C(S-alkyl)=NO-, -C(O-alkyl)-NO-, -SC(=O)O-,
-NHC(=O)O-, -N(alkyl)C(=O)O-, SO, SO2,
-CH2S(O)h-, -CH(alkyl)S(O)h-, -S(O)hCH2-,
-OC(=S)S-, -C(=O)S-, -C(=S)-S-, -NH(alkyl)C(-O)S-,
-O(C=O)S-, -NH-, -N(alkyl)-, -N( R34)-,-SO2NH-,
-SO2N(alkyl)-, -CONH-, -CON(alkyl)-,
-SC(=O)N(alkyl)-, -S-C(=O)NH-, -NHSO2NH-,
-N(alkyl)SO2N(alkyl)-, -N(alkyl)SO2NH-,
-NHSO2N(alkyl)-, -C(O-alkyl)-N-, -C(S-alkyl)-N-,
-CH(halogen)-, -C(alkyl) (halogen)-, -CH(CN)-,
-C(alkyl)(CN)-, -NH(alkyl)NH-, -NH-N(alkyl)-;
-NH-NH-, -N=N-, -C(=O)-, -C(=O)C(=O)-,
-CH(O-alkyl)-, -CH2C(-O)-, -C(-O)CH2,
-CH(alkyl)C(=O)-, -C(=O)CH(alkyl)-, -CH=CH-,
-C(alkyl)=CH-, -CH=C(alkyl)-, -C(alkyl)=C(alkyl)-,
-C(=O)CH=CH-, -P(Y43) ( Y44-alkyl)-, unsubstituted or substituted -P(Y43) ( Y44-aryl) or arylene,
-si'halogen)2-, -Si(alkyl)2, -OC(=O)N(alkyl)-, -OCH2C(=O)N(alkyl)-, -N(alkyl)CON(alkyl)-; -OC(=O)NH-, -NHCONH-, -SO2NHC(-O)NH-, -NHC(=S)NH
Figure imgf000763_0001
wherein h is a value of from 0 to 2 inclusive, R34 represents acyl, alkylsulfonyl, polyhaloalkyl, polyhaloacyl, polyhaloalkylsulfonyl or unsubstituted or substituted aroyl or arylsulfonyl and Y43 and
Y44 are independently O or S; Z7 and Z8 are independently O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y73 and Y74 are the same or different and represent hydrogen, halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, aryl, polyhaloalkylsulfonyl, alkylamino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy and polyhaloalkylsulfonyloxy;
Figure imgf000764_0001
wherein:
B21 represents -CH2C(CH3)2SCH2-,
-CH2CH=C(CH3)OCH2-,
-CH2CH2SCH2CH(CH3)-,
-CH2CH2SCH2CH2-, -CH2SCH2CO-,
-COCH2C(CH3)2CH2CO-,
-COCH2CH(C6H5)CH2CO-,
-CONH(C6H5)CH2CH2O-, -COC(CH3)2NHCO-,
-CH2CH2N(C6H5)CH2CH2-,
-CH2N(C6H5)CH2CH2-, -CH2CH2CH(C6H5)CH2CH2-, -CO(CH2)3CO-, -CO(CH2)2CO-, -COCH2CH(CH3)CH2CO-, -COCH(CH3)CH2CO-,
-COC(CH3)2CH2CO-,
-COC(CH3)2C(CH3)2CO-, -CO(CH2)4CO-,
-CO(CH2)5CO-, -CO(CH2)5CH2-,
-CO(CH2)4CH2-, -CO(CH2)3CH2-,
-CO(CH2)2CH2-, -COCH2SCH2CO-,
-COCH2N(R52)CH2CO-, -COCH2OCH2CO-,
-COCH2SCS-, -COCH=CH-N=CH-,
-CH2CH(C6H5)CH2-N-CH- or -CO2-CH2CH2- wherein R52 represents hydrogen, alkenyl; unsubstituted or substituted aryl or alkaryl; Z9 and Z10 are independently O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y75 and Y76 are the same or different and represent hydrogen, halogen, alkyl, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, amino, alkylamino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino;
Figure imgf000765_0001
R72represents unsubstituted or substituted phenyl or 1- or 2-naphthyl; X31 represents -OCH2-, -CH2-, a covalent bond, -C(halogen)2, -C≡C-, -OCH(alkyl)-,
-OC(alkyl)2, -CH(alkyl)CH(alkyl)-, -CH(alkyl)-,
-C(alkyl)2-, -OCH2CH2-, -CH2CH2-, SO, -S-,
SO2, -CH2S(O)h-, -CH(alkyl)S(O)h-,
-S(O)hCH2-, -CH(halogen)-, -C(alkyl) (halogen),
-CH(CN)-, -C(alkyl)(CN)-, or -C(=O)-, -CH(O-alkyl)-, -CH2C(=O)-, -C(=O)CH , -CH(alkyl)C(=O)-, -C(=O)CH(alkyl)-, -CH=CH-, -C(alkyl)=CH-, -CH=C(alkyl)-, -C(alkyl)=C(alkyl)-, -C(=O)CH=CH-, arylene, -Si(halogen)2-, -Si(alkyl)2,
Figure imgf000766_0001
wherein h is a value of from 0 to 2 inclusive;
Z11 represents O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y77, Y77 and Y79 are the same or different and represent hydrogen,halogen, alkyl, hydroxy, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, alkylamino, amino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino, with the proviso that when Y77 is halogen and
Y79 is hydrogen then Y78 cannot be amino, alkylamino, dialkylamino or acylamino and with the further proviso that when Y77 and Y78 are the same halogen then Y79 cannot be hydrogen or hydroxy;
Figure imgf000767_0001
R73 represents an unsubstituted or substituted, unsaturated or saturated, aromatic or non-aromatic heterocyclic ring system selected from isoxazole, isothiazole, pyrazole, imidazole, 1,2,4-triazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,4,-thiadiazole, 1,3,4-thiadiazole, oxazole, thiazole, benzopyrazole, benzimidazole, benzoxazole, benzothizole, indole, pyrrole, furan, thiophene, benzofuran, benzothiophene, pyridine, pyrimidine, pyridazine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, quinoline, isoquinoline, quinazoline, phthalazine, benzopyridazine, benzopyrazine, carbazole, dibenzofuran, dibenzo-thiophene, benzoxazine, phthalimide, benzopyran, dibenzopyridine, pyridopyridine, pyrazolopyrimidine, tetrahydropyrimidinedione, piperidine, morpholine, tetrahydrofuran, tetrahydrothiophene, pyrrolidine, thiomorpholine, piperidine-2-one, piperidine-2,6-dione, 2,5-pyrrolidinedione, 3-morpholinone, 2-oxohexamethyleneimine, 2-oxotetramethyleneimine, 1-pyrazoline, 2-pyrazoline, pyrazolidine, 2-imidazolidinone, 2-imidazolidinethione, 2,4-imidazolidinedione, 1,2-oxathiolane, 1,3-oxathiolane, 1,3-oxathiane, 1,4-oxathiane, 2(1H)-pyrazinone, 2H-pyran-2-one, 4H-pyran-4-one,
2H-pyran-2-thione, 4H-pyran-4-thione. tetrahydropyran, tetrahydrothiopyran,
7-oxabicyclo[2.2.1]heptane,
7-azabicyclo[2.2.1]heptane, oxetane, coumarin,
1,3-dioxane, 1,4-dioxane or 1,3-dioxolane;
X32 represents -OCH2-, -CH2-, a covalent bond, -C(halogen) , -C≡C-, -OCH(alkyl)-,
-OC(alkyl)2, -CH(alkyl)CH(alkyl)-, -CH(alkyl)-,
-C(alkyl)2-, -OCH2CH2-, -CH2CH2-, SO, -S-.
SO2, -CH2S(O)h-, -CH(alkyl)S(O)h-,
-S(O)hCH2-, -CH(halogen)-, -C(alkyl) (halogen)-,
-CH(CN)-, -C(alkyl)(CN)-, -C(=O)-, -CH(O-alkyl)-, -CH2C(=O)-, -C(=O)CH , -CH(alkyl)C(=O)-, -C(=O)CH(alkyl)-, -CH=CH-, -C(alkyl)=CH-, -CH=C(alkyl)-, -C(alkyl)=C(alkyl)-, -C(=O)CH=CH-, arylene, -Si(halogen)2-, -Si(alkyl)2,
Figure imgf000768_0001
wherein h is a value of from 0 to 2 inclusive;
Z12 represents O, S, C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y8., Y81 and Y82 are the same or different and represent hydrogen, halogen, alkyl, hydroxy, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, alkylamino, amino, dialkylamino, acylamino, acyloxy. alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, phosphono or phosphino;
Figure imgf000769_0001
R74 represents unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl cycloalkenyl, cycloalkadienyl, cycloalkatrienyl, bicycloalkyl, bicycloalkenyl, bicycloalkadienyl, tricycloalkyl, tricycloalkenyl or tricycloalkadienyl;
X33 represents -OCH2-, -CH2-, a covalent bond, -C(halogen) , -C≡C-, -OCH(alkyl)-,
-OC(alkyl)2, -CH(alkyl)CH(alkyl)-, -CH(alkyl)-,
-C(alkyl)2-, -OCH2CH2-, -CH2CH2-, SO, -S-,
SO2, -CH2S(O)h-, -CH(alkyl)S(O)h-,
-S(O)hCH2-, -CH(halogen)-, -C(alkyl) (halogen)-,
-CH(CN)-, -C(alkyl)(CN)-, or -C(=O)-, -CH(O-alkyl)-,
-CH2C(=O)-, -C(-O)CH2, -CH(alkyl)C(=O)-,
-C(=O)CH(alkyl)-, -CH=CH-, -C(alkyl)=CH-,
-CH=C(alkyl)-, -C(alkyl)=C(alkyl)-, -C(=O)CH=CH-, arylene, -Si(halogen)2-, -Si(alkyl)2,
Figure imgf000769_0002
wherein h is a value of from O to 2 inclusive ;
Z13 represents O, S , C1-C8 alkylidene, substituted or unsubstituted benzylidene, NH or NR''' wherein R''' is alkyl, aryl, aralkyl, alkenyl or alkynyl; and
Y83, Y84 and Y85 are the same or different and represent hydrogen, halogen, alkyl, hydroxy, cyano, polyhaloalkyl, alkoxy, polyhaloalkoxy, haloalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, nitro, acyl, polyhaloalkylsulfonyl, alkylamino, amino, dialkylamino, acylamino, acyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkenylsulfonyloxy, haloalkylsulfonyloxy or polyhaloalkylsulfonyloxy; in which the permissible substituents for formulae (i) through (xxxi) above are the same or different and are one or more hydrogen, halogen,alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl , alkoxycarbonylalkylthio , polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, ara.lkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000772_0001
or
Figure imgf000772_0002
R1 - X - R36 (xxxii)
Figure imgf000772_0003
wherein:
Y62, Y63, Y64, Y65 and Y66 are the same or different and are halogen; R1 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylammocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkyls ilyl , aryldialkylsilyl , triarylsilyl , sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, or a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium, -X, = X, -X = R3 , = X-R3
-X - R3
Figure imgf000775_0001
or
; or
Figure imgf000775_0002
R1 is a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylammocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, poiyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3 , = X-R3,
-X - R3 , or
Figure imgf000777_0001
Figure imgf000777_0002
X is a covalent single bond or double bond, a substituted or unsubstituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosplonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkyny , alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3 , -X - R3
Figure imgf000780_0001
or
and
Figure imgf000780_0002
R36 is a substituted or unsubstituted, asymmetrical heterocyclic ring system having at least three nitrogen atoms which is selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl: alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonie acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino. trialkylammonium, arylamino, aryl (alkyl) amino. aralkylamino, alkoxyalkylphosphinyl. alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, =X-R3,
-X - R3
Figure imgf000782_0001
or
Figure imgf000782_0002
wherein:
R3 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which may be saturated or unsaturated in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative. salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsτlfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triary\silyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy. aroyl, haloacyl, polyhaljoacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino. trialkylammonium, arylamino, aryl(alkyl)amino. aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino. aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium -X, = X, -X = R3, = X-R3,
-X - R3 ,
Figure imgf000785_0001
or or
Figure imgf000785_0002
R3 is a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain containing two or more carbon atoms or heteroatoms in any combination in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy. polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X
-X - R3
Figure imgf000787_0001
or
Figure imgf000787_0002
Y1 and Y4 are independently oxygen or sulfur; Y2 and Y3 are independently oxygen, sulfur, amino or a covalent bond; and R4 and R5 are independently hydrogen or substituted or unsubstituted alkyl, polyhaloalkyl, phenyl or benzyl in which the permissible substituents are the same or different and are one or more hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, ' triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino in which the permissible substituents are the same or different and are one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, aIkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloaIkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polyhaloalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycartonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhaloacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl(alkyl)amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, alkylaminoalkoxy, dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkenyl, cyanoalkoxy, dialkylsulfonium,
-X, = X, -X = R3, = X-R3,
-X - R3 ,
or
Figure imgf000789_0001
Figure imgf000790_0001
106. A composition for reducing moisture loss from plants comprising an acceptable carrier and an effective amount, sufficient to reduce moisture loss from plants without substantially inhibiting plant photosynthetic electron transport, of a compound of claim 105.
107. A composition for increasing crop yield comprising an acceptable carrier and an effective amount sufficient to increase crop yield without substantially inhibiting plant photosynthetic electron transport, of a compound of claim 105.
108. The method of claim 1 in which the compound is used in combination with one or more other biologically active compounds.
109. The method of claim 53 in which the compound is used in combination with one or more other biologically active compounds.
110. A method for reducing moisture loss from soil having plants or crops planted therein which comprises applying to the plant surface or crop an effective amount, sufficient to reduce soil moisture loss without substantially inhibiting plant photosynthetic electron transport, of a compound having the formula R1 - X - R2 wherein R1, X and R2 are as defined in claim 1.
PCT/US1987/000240 1986-01-23 1987-01-23 Use of heterocyclic nitrogen-containing compounds for reducing moisture loss from plants and increasing crop yield WO1987004321A2 (en)

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HU871236A HUT45848A (en) 1986-01-23 1987-01-23 Applications of heterocyclic nitrogen-containing compounds for reducing water loss of plants and for increasing crop yield
BR8705356A BR8705356A (en) 1986-01-23 1987-01-23 PROCESS FOR THE PREPARATION OF AGRICULTURAL COMPOSITIONS TO REDUCE THE LOSS OF WATER BY THE PLANTS DUE TO TRANSPIRATION, CONTAINING HEXAGONAL NITROGENIZED HETAGOCYCLIC OR PENTAGONAL DERIVATIVES
FI874111A FI874111A0 (en) 1986-01-23 1987-09-21 ANVAENDNING AV HETEROCYKLISKA, KVAEVE INNEHAOLLANDE FOERENINGAR FOER ATT MINSKA FUKTAVDUNSTNING FRAON PLANTOR OCH ATT OEKA SKOERDERESULTAT.
KR870700857A KR880700635A (en) 1986-01-23 1987-09-22 Use of heterocyclic nitrogen-containing compounds to reduce plant water loss and increase crop yield
DK496187A DK496187A (en) 1986-01-23 1987-09-22 HETEROCYCLIC NITROGEN CONNECTIONS AND THEIR APPLICATIONS TO REDUCE LOSS OF PLANT HUMIDITY AND PROGRESS OF CROP YIELD

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US6265411B1 (en) 1996-05-06 2001-07-24 Zeneca Limited Oxindole derivatives
US6291455B1 (en) 1996-03-05 2001-09-18 Zeneca Limited 4-anilinoquinazoline derivatives
US6294532B1 (en) 1997-08-22 2001-09-25 Zeneca Limited Oxindolylquinazoline derivatives as angiogenesis inhibitors
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US6184225B1 (en) 1996-02-13 2001-02-06 Zeneca Limited Quinazoline derivatives as VEGF inhibitors
US6291455B1 (en) 1996-03-05 2001-09-18 Zeneca Limited 4-anilinoquinazoline derivatives
US6265411B1 (en) 1996-05-06 2001-07-24 Zeneca Limited Oxindole derivatives
USRE42353E1 (en) 1996-09-25 2011-05-10 Astrazeneca Uk Limited Quinazoline derivatives and pharmaceutical compositions containing them
US6897210B2 (en) 1996-09-25 2005-05-24 Zeneca Limited Quinazoline derivatives and pharmaceutical compositions containing them
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PT84183A (en) 1987-02-01
PT84183B (en) 1989-09-14
OA08675A (en) 1989-03-31
FI874111A (en) 1987-09-21
FI874111A0 (en) 1987-09-21
KR880700635A (en) 1988-04-11
AU7031687A (en) 1987-08-14
EP0258391A1 (en) 1988-03-09
IL81307A0 (en) 1987-08-31
DK496187A (en) 1987-09-22
GR870094B (en) 1988-09-28

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