EP0261226A1 - Utilisation de composes derives d'acide malonique afin d'augmenter les recoltes - Google Patents

Utilisation de composes derives d'acide malonique afin d'augmenter les recoltes

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Publication number
EP0261226A1
EP0261226A1 EP87902946A EP87902946A EP0261226A1 EP 0261226 A1 EP0261226 A1 EP 0261226A1 EP 87902946 A EP87902946 A EP 87902946A EP 87902946 A EP87902946 A EP 87902946A EP 0261226 A1 EP0261226 A1 EP 0261226A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
substituted
ring system
unsubstituted
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP87902946A
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German (de)
English (en)
Inventor
Charles David Fritz
Anson Richard Cooke
David Treadway Manning
James Joseph Cappy
Thomas Neil Wheeler
Barbara Auxier Moore
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhone Poulenc Nederland BV
Rhone Poulenc BV
Original Assignee
Rhone Poulenc Nederland BV
Rhone Poulenc BV
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Publication of EP0261226A1 publication Critical patent/EP0261226A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/12—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
    • C07C233/15—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • A01N37/04—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof polybasic
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/30—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the groups —CO—N< and, both being directly attached by their carbon atoms to the same carbon skeleton, e.g. H2N—NH—CO—C6H4—COOCH3; Thio-analogues thereof
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C233/07—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more 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
    • C07D261/14—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or 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
    • C07D277/38—Nitrogen atoms
    • C07D277/44—Acylated amino or imino radicals
    • C07D277/46—Acylated amino or imino radicals by carboxylic acids, or sulfur or nitrogen analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles 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 in position 2
    • C07D277/82—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
    • C07D285/135—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms

Definitions

  • This invention relates to the use of malonic acid derivative compounds for increasing crop yield. This invention further relates to novel malonic acid derivative compounds and processes for the preparation thereof.
  • malonic acid derivative compounds have been known for some time in the art. See, for example, U.S. Patent 2,504,896 and U.S. Patent 3,254,108. Some malonic acid derivative compounds have been described in the art as capable of providing certain plant growth regulating responses such as prevention of fruit drop, rooting of cuttings and formation of parthenogenetic fruit.
  • U.S. Patent 3,072,473 describes N-arylmalonamic acids and their esters and salts, N, N'-diarylmalonamides, N-alkyl-N-arylmalonamic acids and their esters and salts, and N, N'-dialkyl-N, N'-diarylmalonamides which may be useful as plant growth reguiants and herbicides.
  • Japanese Patent 84 39,803 (1984) describes malonic acid anilide derivative compounds which may be useful as plant growth regulators. The plant growth regulating properties of substituted malonyl monoanilides are described by Shindo, N. and Kato, M., Meiji Daigaku Noogaku-bu Kenkyu Hokoku, Vol. 63, pp. 41-58 (1984).
  • This invention relates to a method for increasing crop yield which comprises applying to the crop an effective amount, sufficient to increase crop yield, of a compound having the formula:
  • This invention also relates to novel malonic-sacId derivative compounds and to processes for the prepartion of said compounds.
  • this invention relates to a method of increasing crop yield by use of certain malonic add derivative compounds. More particularly, this invention involves a method for increasing crop yield which comprises applying to the crop an effective amount, sufficient to increase crop yield, of a compound having the formula: wherei n :
  • R 1 and R 2 are independently 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, formyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthlo, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dlalkylsulfamid
  • R 1 and R 2 are independently hydrogen or derivative salts, or 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 Z as hereinbefore defined;
  • Y 1 and Y 2 are independently a substituted or unsubstituted heteroatom in which the permissible substituents are Z as hereinbefore defined; Y 3 and Y 4 are independently hydrogen, or 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, or halogen, alkylcarbonyl, formyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkyIthio, polyhaloalkenylthio, thiocyano, propargylthio, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl,
  • Y 5 and Y 6 are independently oxygen or sulfur;
  • 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 Z as hereinbefore defined;
  • 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 Z as hereinbefore defined;
  • 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 substituent
  • the alkyl-containlng moieties in formula 1 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.
  • R 1 and R 2 are independently other than hydrtogen, alkyl or aryl when both Y 1 and Y 2 are
  • hydrogen or derivative salts refer to hydrogen or any appropriate derivative salt substituents which may be substituted therefore.
  • Illustrative derivative salt substituents include, for example, ammonium, alkylammonium, polyalkylammonium, hydroxyalkylammonium, poly(hydroxyalkyl)ammonium, alkali metals, alkaline earth metals and the like including mixtures thereof.
  • Monocyclic ring systems encompassed by R 1 , R 2 and R 3 in formula 1 may be represented by generalized formula 2 as follows:
  • 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 3 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 Y 3 and Y 4 linked together in formula 1 may include any monocyclic ring system of R 1 , R 2 and R 3 appropriately positioned in formula 1.
  • Ring-forming heteroatoms may in some cases bear oxygen atoms as in aromatic N-oxides and ring systems containing the sulfinyl, sulfonyl, selenoxlde and phosphine oxide moieties.
  • Selected carbon atoms contained in cycles formed by B 1 and A 1 containing at least 3 ring-forming atoms may bear carbonyl, thlocarbonyl, 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.
  • Bicycllc ring systems encompassed by R 1 , R 2 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 or 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 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 Y 3 and Y 4 linked together in formula 1 may include any bicyclic ring system of R 1 , R 2 and R 3 appropriately positioned in formula 1.
  • bicyclic ring systems defined for R 1 , R 2 , R 3 and Y 3 and Y 4 linked together 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 , R 2 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 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 carf'n 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 , R 2 , R 3 and Y 3 and Y 4 linked together 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 Y 3 and Y 4 linked together in formula 1 may include any polycyclic ring system of R 1 , R 2 and R 3 appropriately positioned in formula 1.
  • Bridged bicyclic structures encompassed by R 1 , R 2 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 Y 3 and Y 4 linked together in formula 1 may include any bicyclic bridged system of R 1 , R 2 and R 3 appropriately positioned in formula 1.
  • formula 1 encompasses a wide variety of malonic acid derivative compounds.
  • Illustrative malonic acid derivative compounds within the scope of formula 1 which may be used for increasing crop yield are included in Tables 1 through 11 below.
  • novel malonic acid derivative compounds of this invention can be depicted by the following formulae:
  • Y 11 is O, S or NR wherein R 7 is hydrogen or alkyl
  • Y 12 is O, S, NH or N (alkyl); and R 6 is ammonium, alkylammonium, polyalkylammonium, hydroxyalkylammonium, poly(hydroxyalkyl)ammonium, an alkali metal or alkaline earth metal or substituted or unsubstituted hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkylaminoalkyl, dlalkylaminoalkyl, aryl, mercaptoalkyl, alkylthloalkyl, arylthioalkyl, aryloxyalkyl, alkylsulfonylalkyl, alkylsulflnylalkyl, acylalkyl, aroylalkyl, dialkoxyphosphinylalkyl, diaryloxyphosphinylalkyl, hydroxyalkylthioalkyl, hydroxyalkylsulfonylalky
  • Z 2 is independently substituted or unsubstituted halogen, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio.
  • Y 13 is O, S or NR 9 wherein R 9 is hydrogen or alkyl
  • Y 14 is O, S, NH or N (alkyl);
  • Y 15 and Y 16 are Independently hydrogen, alkyl, halogen, alkoxy, alkylthio, alkenyl, alkynyl, hydroxy, cyano, nitro, formyl, amino, alkylcarbonyl, dialkoxyalkyl, alkylcarbonylamino, formylamino, hydroxyalkyl, haloalkyl or polyhaloalkyl provided that when Y 15 is alkyl then Z 2 is not halogen or polyhaloalkyl at the para- position, and further provide that at least one of Y 15 and Y 16 is other than hydrogen;
  • Y 15 and Y 16 may be linked together to form a substituted or unsubstituted 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; and
  • R 8 is hydrogen or R 6 ;
  • Y 17 is O, S or NR 11 wherein R 11 is hydrogen or alkyl
  • Y 18 is O or S
  • Y 19 and Y 20 are independently hydrogen, alkyl, alkoxy, alkylthio, halogen, haloalkyl or polyhaloalkyl; or
  • Y 19 and Y 20 may be linked together to form 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; and
  • R 10 is hydrogen or R 6 ;
  • R 1 and R 2 are independently 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; or
  • R 1 and R 2 are independently hydrogen or derivative salts, or 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;
  • Y 1 and Y 2 are independently a substituted or unsubstituted heteroatom
  • Y 3 and Y 4 are linked together to form 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; and
  • Y 5 and Y 6 are independently oxygen or sulfur; in which the permissible substituents for formulae
  • Novel malonic acid derivative compounds within the scope of formula (iv) above can be depicted by the following formulae:
  • Y 21 is O, S or N R 13 wherein R 13 is hydrogen or alkyl
  • Y 22 is O, S, NH or N (alkyl);
  • Y 23 , Y 24 , Y 25 and Y 26 are independently hydrogen, alkyl or halogen
  • R 12 is hydrogen or R 6 ;
  • Y 27 is O, S or NR 15 wherein R 15 is hydrogen or alkyl
  • Y 28 is O S, NH or N (alkyl);
  • Y 29 , Y 30 , Y 31 , Y 32 , Y 33 and Y 34 are independently hydrogen, alkyl or halogen; and R 14 is hydrogen or R 6 ;
  • Y 35 is O, S or NR 17 wherein R 17 is hydrogen or alkyl
  • Y 36 is O or S; and R 16 is hydrogen or R 6 , in which the permissible substituents for formulae (v) through (vii) are as described for Z above for formulae (i) through (iv).
  • the malonic acid derivative compounds encompassed within formula 1 and the intermediate compounds used in the preparation thereof can be prepared by conventional methods known in the art and many may be available from various suppliers.
  • the novel malonic acid derivative compounds of formulae (i) through (vii) above which may used in the method of this invention may be prepared by reacting appropriate starting ingredients in accordance with conventional procedures described in the art as illustrated below.
  • novel malonic acid derivative compounds of formula (i) can be prepared by the following general reaction scheme:
  • novel malonic acid derivative compounds of formula (ii) can be prepared by the following general reaction scheme:
  • novel malonic add derivative compounds of formula (iii) can be prepared by the following general reaction scheme:
  • R 10 are as defined hereinabove. Reactions of this general type for preparing malonic acid derivative compounds of formula (iii) including process conditions are described for example by Richter,
  • novel malonic acid derivative compounds of formula (iv) can be prepared by the following general reaction scheme:
  • Y 6 are as defined hereinabove. Reactions of this general type for preparing malonic acid derivative compounds of formula (iv) including process conditions are described for example by Richter, G.H., supra, according to the known Schotten-Baumann procedure.
  • novel malonic acid derivative compounds of formula (v) can be prepared by the following general reaction scheme:
  • Y 26 and R 12 are as defined hereinabove.
  • novel malonic acid derivative compounds of formula (vi) can be prepared by the following general reaction scheme:
  • novel malonic acid derivative compounds of formula (vii) can be prepared by the following general-reaction scheme:
  • the malonic acid derivative compounds of formula 1 have been found to significantly increase crop yield in comparison with untreated crops at similar conditions.
  • the malonic acid derivative compounds used in this invention are substantially non-phytotoxic to growing plants.
  • an effective amount of a malonic acid derivative compound for increasing crop yield refers to a yield enhancing effective amount of the compound sufficient to increase crop yield.
  • 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.
  • the amount of compound used preferably does not cause substantial phytotoxicity, e.g., foliar burn, chlorosis or necrosis, to the crop.
  • the compound can preferably be applied to plants and crops at a concentration of from about 0.01 to 15 pounds of compound per acre as more fully described below.
  • 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 can be prepared by dissolving one of these compounds with a nonphytotoxic solvent such as acetone, xylene, nitrobenzene, cyclohexanone or dimethyl formamide 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 can 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 0.001 to about 100 pounds of active ingredient per acre, preferably from about 0.01 to about 15 pounds of active ingredient per acre, and more preferably from about 0.1 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 malonic acid derivative compounds of formula 1 are preferably applied to plants and crops under average or normal growing conditions.
  • the malonic acid derivative compounds used in this invention can be applied during the plant vegetative growth phase or the plant reproductive growth phase to obtain increased crop yield. It may be desirable for some crops to apply the malonic acid derivative compounds at the reproductive growth phase including, for example, the early flower stage, fruit set stage or full flower bloom stage. In other crops, it may be desirable to apply the malonic acid derivative compounds at the vegetative growth phase.
  • the application timing will in general depend upon the particular crop to be treated.
  • An increase in crop yield can be attributable, for example, to various plant growth effects such as increased branching (increased reproductive sites), early pod (fruit) set, increased blossom set and inhibition of blossom (flower and fruit) abscission during early stages of plant reproductive development.
  • increased crop yield refers to an increase in the raw agricultural commodity in terms of harvestable yield, e.g., bushels of seeds, bales of cotton and the like. It may be possible to have an increased harvestable yield for a treated crop in comparison with an untreated crop, yet the total crop biomass may be less for the treated crop.
  • harvestable yield as used herein may be inclusive of total crop biomass, e.g., bushels of corn per acre and the like.
  • Treatment of certain crops such as alfalfa with the malonic acid derivative compounds of formula 1 may also increase the crop nutritional value, e.g., total digestable nutrients (TDN).
  • TDN total digestable nutrients
  • plants and crops refer in general to any agronomic or horticultural crops, ornamentals and turfgrasses.
  • Illustrative of plants and crops which can be treated by the malonic acid derivative compounds of formula 1 according to the method of this invention include, for example, corn, cotton, sweet potatoes, white potatoes, alfalfa, wheat, rye, 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.
  • the malonic acid derivative compounds contemplated herein are effective for increasing crop yields. Such compounds have a high margin of safety in that when used in sufficient amount to provide a yield enhancing effect, they do not burn or injure the crop or plant, and they resist weathering which indudes 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 yield enhancing characteristic of the active ingredient or impart undesirable characteristics, for instance, phytotoxicity, to the active ingredients. Mixtures of the active compounds can be employed if desired as well as combinations of the active compounds with other biologically active compounds or ingredients as indicated above.
  • Example I Preparation of ethyl 3-[(4-fluorophenyl)amino]- 3-oxopropanoate Into a nitrogen-purged, air-stirred reaction flask was charged 4.44 grams (0.04 mole) of 4-fluoroaniline, 4.05 grams (0.04 mole) of triethylamine and 200 mmiliters of tetrahydrofuran solvent. A 6.02 gram (0.04 mole) portion of ethyl malonyl chloride was added rapidly with stirring at room temperature followed by a few milliliters of tetrahydrofuran. The temperature rose to 42°C and triethylamine hydrochloride separated therefrom.
  • Example II In a similar manner Compounds 2-76 were prepared and identified in Table A.
  • Example III Preparation of ethyl 1-(2-methyl-4,5-dichlorophenylaminocarbonyl)cyclopropanecarboxylate Into a nitrogen-purged round bottom flask was charged 5.53 grams (0.03 mole) of 2-methyl-4,5-dichloroaniline, 3.18 grams (0.03 mole) of triethylamine and 190 milliliters of tetrahydrofuran solvent. With vigorous stirring, a 5.55 gram (0.03 mole) portion of ethyl 1-chlorocarbonylcyclopropanecarboxylate prepared in Example XVIII was added in one portion, after which the mixture was stirred at ambient temperature for a six-hour period.
  • Example IV In a manner similar to that employed in Example III, Compounds 78-96 were prepared and identified in Table B.
  • Example V Preparation of 3-[(4-bromo-2-methylphenyl)- amino]-3-oxopropanoic acid
  • a 6.0 gram (0.02 mole) portion of ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate prepared in Example I (Compound No. 75) was dissolved in approximately 80 milliliters of ethanol and 1.2 grams (0.03 mole) of sodium hydroxide pellets were added to the resulting mixture. The mixture was stirred for four hours and then allowed to stand overnight. The mixture was then evaporated to drynoss and water added to give a yellow cloudy solution.
  • Example VI In a manner similar to that employed in Example V, Compounds 98-109 were prepared.
  • Example VII Preparation of 1-(2-methyl-4.5-dichlorophenylaminocarbonyl)cvclopropanecarboxylic acid
  • a solution containing 0.34 gram (0.006 mole) of potassium hydroxide and 0.109 gram (0.006 mole) of water in 80 millniters of ethanol was prepared in a 250 milliliter round bottom flask.
  • a solution of ethyl 1-(2-methyl-4,5-dichlorophenylaminocarbonyl)cyclopropanecarboxylate prepared in Example III in a small volume of ethanol was added and the mixture allowed to stir with warming to room temperature over a 72 hour period.
  • Example IX Preparation of ethyl 1-(4-bromo-2-methylphen ⁇ laminocarbonyl)cyclobutanecarboxylate Into a nitrogen-purged reaction flask was charged 2.74 grams (0.01 mole) of 4-bromo-2-methylaniline and 1.49 grams (0.01 mole) of triethylamine dissolved in 200 milliliters of tetrahydrofuran. With vigorous stirring, 2.80 grams (0.01 mole) of ethyl 1-chlorocarbonylcyclobutanecarboxylate prepared in Example XIX were added and the resulting mixture stirred at ambient temperature for 6 hours. A precipitate of triethylamine hydrochloride was removed by filtration.
  • Example XI Preparation of 1-(3,5-dichlorophenylaminocarbonyl)cyclobutanecarboxylic acid A 2.0 gram (0.006 mole) portion of ethyl 1-(3,5-dichlorophenylaminocarbonyl)cyclobutanecarboxylate prepared in Example X (Compound 130) was hydrolyzed in the presence of water (0.114 gram, 0.006 mole) and ethanolic potassium hydroxide (0.355 gram, 0.006 mole).
  • Example XII In a manner similar to that employed in Example XI, Compounds 136-139 were prepared and identified in Table F below.
  • Example XIII Preparation of ethyl 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopentanecarboxylate
  • Ethyl 1-chlorocarbonylcyclopentanecarboxylate (3.10 grams, 0.02 mole) prepared in Example XX, 4-bromo-2-methylaniline (2.82 grams, 0.02 mole) and triethylamine (1.53 grams, 0.02 mole) were reacted in tetrahydrofuran (200 milliliters) under conditions similar to that described in Example I to give 2.40 grams (0.007 mole) of ethyl 1-(4-bromo-2-methylphenylaminocarbonyl)cyclopentanecarboxylate (Compound 140) which, after recrystallization from hexane, had a melting point of 64°C-67oC.
  • Example XIV Preparation of ethyl 2-(4-bromo-2- methylphenylaminocarbonyl)butanoate
  • Ethyl 2-(chlorocarbonyl)butanoate (5.8 grams, 0.03 mole), 4-bromo-2-methylaniline (5.0 grams, 0.03 mole) and triethylamine (3.27 grams, 0.03 mole) were reacted under conditions similar to that described for Example I to give 7.4 grams (0.02 mole) of ethyl 2-(4-bromo-2-methylphenylaminocarbonyl)butanoate (Compound 141) as a white solid having a melting point of 98°C-100°C.
  • Example XV In a manner similar to Example XIV, Compounds 142-152 were prepared and identified in Table G below.
  • Example XVI Preparation of 3-[(4-bromo-2-methylphenyl)- amino]-2-bromo-2-methyl-3-oxopropanoic acid
  • Example XVII Preparation of N-butyl 3-[(4-bromo-2- methylphenyl)amino]-3-oxopropanamide
  • Example XIX Preparation of ethyl 1-chlorocarbonylcyclobutanecarboxylate Diethyl 1,1-cyclobutanedicarboxylate (20.0 grams, 0.10 mole) was saponified with 6.59 grams (0.10 mole) of potassium hydroxide in a mixture of 200 milliliters of ethanol and 1.80 grams (0.10 mole) of water and worked up to give the monocarboxylic acid which was reacted with thionyl chloride (8.86 grams, 0.07 mole) in methylene chloride solution as described in Example XVIII.
  • Example XX Preparation of ethyl 1-chlorocarbonylcyclopentanecarboxylate
  • a 10 gram (0.05 mole) portion of diethyl 1,1-cyclopentanedicarboxylate was converted into 5.67 grams (0.03 mole) of ethyl 1-chlorocarbonylcydopentanecarboxylate (Compound 157).
  • NMR analysis of the product indicated the following:
  • Example XXII Preparation of ethyl 3-[(4-chlorophenyl)amino1-3- oxopropanoate 4-Chloroanlline (25.4 grams, 0.20 mole) and diethyl malonate (48 grams, 0.30 mole) were reacted in a manner similar to the procedure described by A.K. Sen and P. Sengupta, Jour. Indian Chem. Soc. 46 (9), 857-859 (1969).
  • Example XXIII Preparation of ethyl 3-[(4-methylthiazol-2-yl) aminol-3-oxopropanoate
  • 2-amino-4-methylthiazole was reacted with ethyl malonyl chloride employing triethylamine as the acid acceptor in tetrahydrofuran solution.
  • the ethyl 3-[(4-methylthiazol-2-y1)amino]-3-oxopropanoate product (Compound 160) (7.5 grams, 0.03 mole) was obtained as an off-white solid having a melting point of 138°C-141°C.
  • Example XXIV In a manner similar to Example XXIII, Compounds 161-173 were prepared and identified in Table H below.
  • Example XXV Preparation of ethyl 2-chlorocarbonyl-3- methyl-2-butenoate Diethyl isopropylidenemalonate (30 grams, 0.15 mole) was saponified with 10.0 grams (0.15 mole) of potassium hydroxide in 200 milliliters of ethanol solution and worked up to give the monocarboxylic acid which was then reacted with thionyl chloride (10 mllimters, 0.1 mole) in methylene chloride solution in a manner similar to the procedure described in Example XVIII. Removal of solvent gave 9.6 grams (0.05 mole) of ethyl 2-chlorocarbonyl-3-methyl-2-butenoate. NMR analysis of the residue product in CDCI 3 solution indicated complete conversion of the carboxylic acid to the acid chloride as evidenced by absence of a downfield carboxylic acid proton. This compound is referred to hereinafter as Compound 174.
  • Example XXVI Preparation of ethyl 2-[(4-bromo-2-methylphenyl)- aminocarbonyl]-3-methyl-2-butenoate
  • ethyl 2-chlorocarbonyl-3-methyl-2-butenoate 9.6 grams, 0.05 mole
  • 4-bromo-2-methylaniline 5.3 grams, 0.03 mole
  • triethylamine 4.0 mnimters, 0.03 mole
  • Example XXVII Preparation of 3,4-dichloro-2,5-dimethylannine A solution of 5.0 grams (0.03 mole) of 3,4-dichloro-2,5-dimethyl-1-nitrobenzene in 70 milliliters of ethanol was hydrogenated at room temperature at 50 psi in the presence of 0.25 gram of 10% palladium on activated carbon as a catalyst. Working up the reaction mixture gave 1.21 grams (0.006 mole) of 3,4-dichloro-2,5-dimethylaniline (Compound 176) as a yellow solid having a melting point of 72°C-76°C.
  • Part A Preparation of 2,2-dimethyl-N-(4-chloro- 2-metho ⁇ yphenyl)propanamide
  • the resulting mixture was stirred for two hours at room temperature.
  • Triethylamine hydrochloride precipitated and was filtered off and the filtrate vacuum stripped to give a dark liquid which was taken up in methylene chloride.
  • Part B Preparation of 2,2-dimethyl-N- (4,5-dichloro-2-methoxyphenyl)propanamide Into a stirred solution containing 6.82 grams (0.03 mole) of 2,2-dimethyl-N-(4-chloro-2-methoxyphenyl)propanamide prepared in Part A in 150 miliniters of chloroform was added 3.81 grams (0.03 mole) of sulfuryl chloride over a 40 minute period. The resulting reaction mixture was heated under reflux for a 3 day period, each day cooling the mixture and adding an additional 3.81 grams (0.03 mole) of sulfuryl chloride before continuing the reflux. At the end of 3 days, thin layer chromatographic analysis of the mixture indicated the reaction to be complete.
  • Part C Preparation of 4.5-dichloro-2- methoxyanlline
  • the 2,2-dimethyl-N-(4,5-dichloro-2-methoxyphenyl)propanamide (3.70 grams, 0.01 mole) prepared in Part B was dissolved in ethanol: 12N HCl (1:1), the mixture heated under reflux overnight and then freed of volatiles under rotary evaporation.
  • Example IX A 3.0 gram (0.009 mole) portion of ethyl l-(4-bromo-2-methylphenylaminocarbonyl)cyclobutanecarboxylate prepared in Example IX (Compound 129) was hydrolyzed in a manner similar to that described in Example XI to give 2.19 grams (0.007 mole) of 1-(4-bromo-2-methylphenylaminocarbonyl)cyclobutanecarboxylic acid, Compound 181, having a melting point of 154°C-155°C.
  • Example LIII 3,5-Dichloroaniline (2.69 grams, 0.02 mole) and ethyl (chlorocarbonyl)methoxyacetate (3.0 grams, 0.02 mole), prepared in Example LIII (Compound 211), were reacted in the presence of triethylamine (1.68 grams, 0.02 mole) in 200 milliliters of methylene chloride in a manner similar to that described in Example I to give 1.34 grams (0.004 mole) of ethyl 3-[(3,5-dichlorophenyl)amino]-2-methoxy-3-oxopropanoate, Compound 213, having a melting point of 89.5°C-92.5°C.
  • Dimethyl methoxymalonate (50.0 grams, 0.3 mole) was saponified with potassium hydroxide (17.3 grams, 0.3 mole) in a mixture of 500 milliliters of methanol and 5.55 grams (0.3 mole) of water according to the general procedure of Example VII but employing a reaction period of approximately 16 hours.
  • the reaction mixture was evaporated free of solvents and the residue dissolved in water and extracted twice with ether to remove any unreacted diester.
  • the aqueous layer was then saturated with potassium chloride, acidified with 2H HCl and extracted twice with ethyl ether.
  • t-Butyl methyl methoxymalonate (7.57 grams, 0.04 mole), prepared in Part A, was saponified with potassium hydroxide (2.45 g, 0.04 mole) in a mixture of 25 milliliters of methanol and 668 microliters (0.04 mole) of water according to the general procedure of Example VII but employing a reaction period of 20 hours. Workup according to the general method of Example VII gave 5.42 grams (0.03 mole) of mono-t-butyl methoxymalonate. NMR analysis of the product indicated the following:
  • a 50 milliliter round-bottom flask was equipped with a magnetic stirring bar and a reflux condenser with N 2 inlet.
  • the flask was charged with 183.0 grams (1.07 mole) of bis(trimethylsilyl) acetylene and 0.40 gram (0.001. mole) of cupric acetylacetonate.
  • Using an oil bath the temperature of the stirred mixture was raised to 145°C.
  • Using a syringe pump 39.3 grams (0.21 mole) of diethyl diazomalonate were added over 36 hours. Heating at 1450C was continued for an additional 12 hours after all of the diazomalonate had been added.
  • the excess bis(trimethylsilyl)acetylene was removed by vacuum distillation.
  • a 500 milliliter round-bottom flask was equipped with a magnetic stirrer and N 2 inlet.
  • the flask was charged with 21.0 grams (0.07 mole) of diethyl bis (2,3-trimethylsilyl)cyclopropene-1,1-dicarboxylate, 125 milliters of acetonitrile, 12.2 grams (0.21 mole) of anhydrous KF, and 6.50 grams (0.02 mole) of dicyclohexano-18-crown-6 ether.
  • the mixture was stirred 6 hours at room temperature.
  • the mixture was filtered and the filtrate concentrated under reduced pressure to a deep red oil. This oil was taken up in 100 milliliters of methanol and stirred 24 hours at room temperature.
  • a 250 milliliter round-bottom flask was equipped with a magnetic stirring bar and an addition funnel with N 2 inlet.
  • the flask was charged with 6.15 grams (0.03 mole) of diethylcyclopropene-1,1-dicarboxylate and 50 milliliters of ethanol.
  • the stirred mixture was cooled in an ice bath and a solution of 1.33 grams (0.03 mole) of NaOH in 5.0 milliliters of water was added dropwise.
  • the mixture was allowed to come to room temperature and stirred for 3 days.
  • the reaction mixture was concentrated to 1/4 of the original volume under reduced pressure, diluted with ice water, and extracted twice with ether.
  • the flask was charged with1.30 grams (0.008 mole) of mono-ethyl cyclopropene-1,1-dicarboxylate, 50 milliliters of dry THF, 2.3 grams (0.02 mole) of potassium carbonate (anhydrous), and 450 milligrams of dicyclohexano-18-crown-6 ether.
  • the stirred reaction mixture was cooled to 00C, and 0.90 gram (0.008 mole) of ethyl chloroformate in 10 milliliters of THF was added dropwise. The mixture was stirred for 2 1/2 hours at 00C.
  • Plant axillary stimulation may be indicative of increased plant reproductive sites resulting in increased plant biomass and/or increased crop yield. Treatment of plants with certain malonic acid derivative compounds such as those compounds identified in Table I below results in enhanced axillary stimulation.
  • Solutions of the test compounds identified in Table I were prepared by dissolving 68.8 milligrams of the particular compound in 5.5 milliliters of acetone and then adding water to a final volume of 11.0 miimiters. 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 6255 parts per million by weight of the particular compound.
  • the test concentrations in parts of the test compound per million parts by weight of final solution employed in the axillary stimulation tests in Table I were obtained by appropriate dilution of the stock suspensions with acetone and water (50/50 volume/volume).
  • a water-acetone solution containing no test compound was also sprayed on a flat.
  • all of the flats of plants were placed in a greenhouse at a temperature of 80°F ⁇ 5°F and humidity of 50 percent ⁇ 5 percent.
  • Visual Indications of axillary stimulation activity were observed and recorded 10 to 14 days after treatment.
  • Enhancement-Wheat Solutions of Compound 75 were prepared by dissolving either 0.48 grams, 0.96 grams or 1.92 grams of the compound into 800 milliliters acetone. Water plus 0.2 percent by volume of Surfelk spray adjuvant were added to each of the above solutions to a final volume of 1600 milliliters. Surfelk spray adjuvant is commercially available from Union Carbide Corporation, Danbury, Connecticut.
  • the above formulations were applied to each plot by use of a carbon dioxide backpack sprayer set at about 30 psig air pressure.
  • the planting, application and harvesting times for each crop are detailed in Table J.
  • the harvested wheat crops for yield determination included the inner 20 feet of the middle 4 rows in each plot (5 feet in from ends of the middle 4 rows). The values obtained for each plot in each repetition were averaged to obtain the results in Table J.
  • Solutions of Compound 75 were prepared by dissolving either 70 milligrams, 140 milligrams or 280 milligrams of the compound into 87 milliliters of acetone. Water plus 0.2 percent by volume of Triton X-100 surfactant were added to each of the above solutions to a final volume of 174 milliliters. Triton X-100 surfactant is commercially available from Rohm and Haas Company, Phildelphla, Pennsylvania.
  • the above formulations were applied to each plot by use of a carbon dioxide backpack sprayer set at about 30 psig air pressure.
  • the planting, applicaton and harvesting times are detailed in Table L.
  • the harvested soybean crops for yield determinaton included the inner 10 feet of the middle 2 rows in each plot (5 feet in from ends of the middle 2 rows).
  • the values obtained for each plot (kilograms of soybeans/plot) in each repetition were averaged to obtain the results in Table L.
  • Table L demonstrate that treatment of soybean plants with certain malonic acid derivative compounds at certain rates provides significantly increased yields in comparison with untreated control soybean plants. As demonstrated in Table L, in addition to an increase in actual yield (kilograms of soybeans/plot), the treated soybean plants exhibited an increased number of pods per plant in comparison with untreated control soybean plants.
  • Solutions of Compound 75 were prepared by dissolving either 0.75 grams or 1.5 grams of the compound into 125 milliliters acetone. Water was added to each of the above solutions to a final volume of 250 milliliters.
  • Table M demonstrate that treatment of soybean plants with certain malonic acid derivative compounds at certain rates provides significantly increased yields in comparison with untreated control soybean plants. As demonstrated in Table M, in addition to an increase in actual yield (kilograms of soybeans/plot), the treated soybean plants exhibited an increased number of pods per plant in comparison with untreated control soybean plants.
  • Example XLIII Effect of Representative Malonic Acid Derivative Compounds on Crop Yield Enhancement-Snapbeans Solutions of Compound 75 were prepared by dissolving either 1.56 milligrams, 3.13 milligrams or 6.25 milligrams of the compound in 5 milliliters of acetone and then adding water to a final volume of 10 milliliters.
  • Increased chlorophyll content can be an indication of increased photosynthetic activity resulting in increased biomass and/or increased crop yield.
  • Treatment of plants with certain malonic acid derivative compounds, e.g., Compound 75, as described hereinafter results in enhanced levels of chlorophyll.
  • Solutions of Compound 75 were prepared by dissolving either 1.56 milligrams, 6.25 milligrams or 25.0 milligrams of the compound in 5 milliliters of acetone and then adding water to a final volume of 10 milliliters.
  • Nitrate reductase is a substrate-lnducible enzyme which mediates the conversion of nitrate to nitrite.
  • the inducible nature of nitrate reductase and the dependence of the enzyme level on substrate level provides the plant with a mechanism for controlling growth.
  • Nitrate reductase catalyzes the rate-limiting step in the conversion of nitrate into proteins.
  • increased levels of nitrate reductase may indicate increased potential for grain and protein production. See, for example, Beevers, L. and R.H. Hageman, 1969, Nitrate Reduction in Higher Plants, Annual Review of Plant Physiology 20: 495-522.
  • Solutions of Compound 75 were prepared by dissolving either 1.56 milligrams, 6.25 milligrams or 25.0 milligrams of the compound 1n 5 milliliters of acetone and then adding water to a final volume of 10 milliliters.
  • nitrate released into the medium was determined by removing a 0.2 milliliter aliquot from each beaker and placing it in a test tube. Into the test tube was added 0.25 milliliters of 1 percent (weight/volume) sulfanilamide in 3N HCl and 0.25 milliliters of 0.02 percent (weight/volume) N-(1-naphthyl)- ethylenediamine dihydrochloride.
  • test tubes were allowed to stand for 20 minutes before mesuring the optical densities at 540 nanometers on a Beckman DB spectrophotometer.
  • Nitrate reductase activity was expressed as micromoles ( M) of nitrite formed per gram of fresh leaf weight per hour.
  • the values obtained for the control and Compound 75 were averaged to obtain the results in Table P below.
  • Test compounds identified in Table Q below were prepared by dissolving the compounds in acetone/water (50:50 volume/volume) containing 0.05 percent volume/volume of Triton X-100 surfactant commercially available from Rhom and Haas Company, Philadelphia, Pennsylvania. As detailed below, these solutions of test compounds were applied to wheat at a concentration of 0.06, 0.12, 0.25, 0.50 and 1.0 pounds of active ingredient per acre.
  • Wheat seeds (var. Olaf) were planted in a sandy loam soil in flats having the following dimensions: 5.5 inches In width x 9.0 inches in length x 3.0 inches in height. The wheat seeds were sown in 2 different arrangements as follows: 4 rows (5 inches in length) per flat, 10 seeds per row (Flat No. 1); and 2 rows (5 inches in length) per flat, 5 seeds per row (Flat No. 2). Eleven days after planting at the 2-3 leaf growth stage of wheat, each concentration of the test compounds identified in Table Q was applied to a separate flat as a foliar spray by use of an aspirated spray apparatus set at 10 psig air pressure (all flats sprayed at a concentration of 120 gallons per acre).
  • the number of vegetative shoots per seed was determined by actual count. The results reported in Table Q reflect the average of 3 repetitions. The percent increase tillering is based upon the untreated control.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Composés dérivés d'acide malonique, procédés pour leur préparation et leur utilisation afin d'augmenter les récoltes.
EP87902946A 1986-03-31 1987-03-30 Utilisation de composes derives d'acide malonique afin d'augmenter les recoltes Withdrawn EP0261226A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US84643586A 1986-03-31 1986-03-31
US846435 1986-03-31
US1714987A 1987-03-04 1987-03-04
US17149 1987-03-04

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EP0261226A1 true EP0261226A1 (fr) 1988-03-30

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EP (1) EP0261226A1 (fr)
JP (1) JPS63503070A (fr)
KR (1) KR880701223A (fr)
AU (1) AU7284387A (fr)
FI (1) FI875278A0 (fr)
HU (1) HUT47898A (fr)
IL (1) IL82055A0 (fr)
OA (1) OA08946A (fr)
PL (1) PL264912A1 (fr)
PT (1) PT84597A (fr)
WO (1) WO1987005897A2 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5292937A (en) * 1986-03-31 1994-03-08 Rhone-Poulenc Inc. Use of malonic acid derivative compounds for retarding plant growth
HU201455B (en) * 1986-03-31 1990-11-28 Rhone Poulenc Bv Synergetic compositions regulating the growth of plants
WO1987005898A2 (fr) * 1986-03-31 1987-10-08 Rhone-Poulenc Nederlands B.V. Utilisation de composes derives de l'acide malonique pour retarder la croissance des plantes
JP2715559B2 (ja) * 1989-06-26 1998-02-18 富士電機株式会社 高電圧発生回路
EP1033365B1 (fr) 1999-03-03 2002-09-25 Basf Aktiengesellschaft Composé de diuréides et leur utilisation
EP2052612A1 (fr) 2007-10-24 2009-04-29 Bayer CropScience AG Combinaison d'herbicide
DE102008037629A1 (de) 2008-08-14 2010-02-18 Bayer Cropscience Ag Herbizid-Kombination mit Dimethoxytriazinyl-substituierten Difluormethansulfonylaniliden
CN102531787B (zh) * 2012-01-17 2013-07-17 山东省农业科学院作物研究所 一种提高小麦干热风抗性的制剂及其应用方法
DK3157916T3 (en) 2014-06-19 2019-03-18 Ariad Pharma Inc HETEROARYL COMPOUNDS FOR CHINESE INHIBITION

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DE408515C (de) * 1922-02-10 1925-01-19 Anilin Fabrikation Ag Verfahren zur Darstellung eines Esters der 4-AEthoxyphenylmalonamidsaeure
US3072473A (en) * 1959-10-07 1963-01-08 Us Rubber Co Plant growth regulants
US3254108A (en) * 1963-02-18 1966-05-31 Eastman Kodak Co Process for preparation of arylimino propionates
US4021224A (en) * 1971-12-09 1977-05-03 Stauffer Chemical Company Herbicide compositions
US4210647A (en) * 1979-06-18 1980-07-01 Eli Lilly And Company Antiviral combinations
HU201455B (en) * 1986-03-31 1990-11-28 Rhone Poulenc Bv Synergetic compositions regulating the growth of plants

Non-Patent Citations (1)

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Title
See references of WO8705897A2 *

Also Published As

Publication number Publication date
JPS63503070A (ja) 1988-11-10
FI875278A (fi) 1987-11-30
KR880701223A (ko) 1988-07-26
WO1987005897A2 (fr) 1987-10-08
PL264912A1 (en) 1988-07-21
PT84597A (en) 1987-04-01
AU7284387A (en) 1987-10-20
IL82055A0 (en) 1987-10-20
WO1987005897A3 (fr) 1988-04-07
HUT47898A (en) 1989-04-28
FI875278A0 (fi) 1987-11-30
OA08946A (fr) 1990-11-30

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