EP0741714A1 - 2-oxa et thia-zolines arthropodicides - Google Patents

2-oxa et thia-zolines arthropodicides

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Publication number
EP0741714A1
EP0741714A1 EP95908447A EP95908447A EP0741714A1 EP 0741714 A1 EP0741714 A1 EP 0741714A1 EP 95908447 A EP95908447 A EP 95908447A EP 95908447 A EP95908447 A EP 95908447A EP 0741714 A1 EP0741714 A1 EP 0741714A1
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EP
European Patent Office
Prior art keywords
group
alkyl
haloalkyl
optionally substituted
independently selected
Prior art date
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Application number
EP95908447A
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German (de)
English (en)
Inventor
Victor Ekow Amoo
Renee Marie Lett
George Chihshu Chiang
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of EP0741714A1 publication Critical patent/EP0741714A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D263/28—Nitrogen atoms not forming part of a nitro radical
    • 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
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • JP 05001060 discloses 4-thienyl-2-oxa(thia)zoline derivatives wherein the thienyl moiety is bonded directly to the oxa- or thia-zoline ring.
  • U.S. 5,141,948 discloses oxa- and thia-zoline derivatives wherein the left hand phenyl ring is appended to the oxa- or thia-zoline ring either directly or through a lower alkylene bridge. Neither of these references suggests the compounds of the instant invention.
  • This invention pertains to compounds of Formula I, including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use to control arthropods in both agronomic and nonagronomic environments.
  • the compounds are:
  • B is selected from the group O and N-Y;
  • E is selected from the group alkyl and C j -C haloalkyl;
  • X 1 and Z are independently selected from the group O and S;
  • X 2 is selected from the group H, halogen, C ] -C 4 alkyl, C j -C 4 haloalkyl, C1-C 4 alkoxy, C--C 4 haloalkoxy, C r C 4 alkylthio, C(O)OR 13 and CN;
  • Y is selected from the group H, C--C 6 alkyl, C ] -C 6 haloalkyl, 2-C alkenyl, C 2 -C 6 haloalkenyl, C -Cg alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C 4 -C 7 cycloalkylalkyl, CHO, C(O)R 16 , C(O)OR 16 , C(S)R 16 ,
  • X is selected from the group O and S;
  • G 2 is selected from the group single bond, O, S and N-Y;
  • G 3 is selected from the group single bond, O and N-Y;
  • G 4 is selected from the group single bond, O and N-Y;
  • G 5 is selected from the group single bond, O, S and N-Y;
  • G 6 is selected from the group C2-C4 alkenylene, C2-C4 alkynylene, O-C2-C4 alkenylene and O-C2-C4 alkynylene;
  • Q is selected from the group H and J; or Q is selected from the group C ⁇ -C j 6 alkyl, C ] -C 16 haloalkyl, C 2 -C 16 alkenyl, C 2 -C 16 haloalkenyl, C 2 -C 16 alkynyl, C 2 -C ] 6 haloalkynyl, C3-C7 cycloalkyl, C3-C7 halocycloalkyl and C4-C7 cycloalkylalkyl, each group optionally substituted with 1-4 substituents independently selected from W; J is a 5- or 6-membered aromatic ring containing 0 to 4 heteroatoms independently selected from the group 0-4 nitrogen, 0-1 oxygen, and 0-1 sulfur; or J is a 9- to 14-membered aromatic ring system selected from the group fused bicylic ring and fused tricylic ring, each ring system containing 0 to 6 heteroatoms independently selected from the group
  • R 1 is selected from the group halogen, C r C 6 alkyl, C j -C 6 haloalkyl, C r C 6 alkoxy, C--C 6 haloalkoxy, S(O) t R 16 , CN and NO 2 ;
  • R 2 is selected from the group H, halogen, C ] -C 6 alkyl, C j -C 6 haloalkyl, C ] -C 6 alkoxy, C r C 6 haloalkoxy, S(O) t R 16 , CN and NO 2 ;
  • R 3 is selected from the group halogen, Cj-C 16 alkyl, C r C 16 haloalkyl, C 2 -C 16 alkenyl, C 2 -C ] 6 haloalkenyl, C 2 -C 16 alkynyl, C 2 -C 16 haloalkynyl, C 2 -C 16 alkoxyalkyl, C 2 -C 16 alkylthioalkyl, C r C 16 nitroalkyl, C 2 -C 16 cyanoalkyl, C 3 -C- 8 alkoxycarbonylalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, CN, N 3 , SCN, NO 2 , SH, S(O) t R 16 , OCHO, OR 20 , CHO, C(O)R 21 , C(O)OR 21 , C(O)NR 16 R 17 , S(O) 2 NR 16 R
  • R 10 and R 1 are taken together as (CH 2 ) 4 or (CH 2 ) 5 ;
  • R 12 is C,-C ] 8 alkyl
  • R 13 is C r C 4 alkyl
  • R 14 and R 15 are independently C j -C 4 alkyl; or
  • R 14 and R 15 are taken together as (CH 2 ) 4 , (CH 2 ) 5 or CH2CH2OCH2CH2;
  • R 16 is selected from the group C r C 6 alkyl, C j -Cg haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 2 -C 6 alkoxyalkyl, C -C 6 alkylthioalkyl, C r C 6 nitroalkyl, C 2 -C 6 cyanoalkyl, C 3 -C 8 alkoxycarbonylalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C4-C7 cycloalkylalkyl, optionally substituted phenyl and optionally substituted benzyl wherein the phenyl and benz
  • R 17 is selected from the group H and C ] -C4 alkyl; or R 16 and R 17 , when attached to the same atom, are taken together as (CH 2 ) 4 , (CH 2 ) 5 or
  • R 18 is selected from the group C]-C3 alkyl and phenyl optionally substituted with 1-3 substituents independently selected from W- ;
  • R 19 is selected from the group halogen, CN, NO 2 , C r C 6 alkyl, C r C 6 haloalkyl, OR 9 , • C(O)R 16 , C(O)OR 16 and Si(R 6 )(R 7 )(R 8 );
  • R 20 is selected from the group H, C ] -C 4 alkyl, C J -C4 haloalkyl, C 2 -C alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, C(O)R 16 , C(O)OR 16 , C(O)NR 16 R 17 , S(O) 2 NR- 6 R 17 and S(O) 2 R 16 ;
  • R 21 is selected from the group C j -Cg alkyl, C j -Cg haloalkyl, C 2 -Cg alkenyl, C
  • J 1 is selected from the group phenyl and naphthyl, each optionally substituted with 1-4 substituents independently selected from R 19 ; or J 1 is a 5-or 6-membered aromatic ring, attached through carbon or nitrogen, containing 1 to 4 heteroatoms independently selected from the group 1-4 nitrogen, 0-1 oxygen, and 0-1 sulfur, the ring optionally substituted with 1-4 substituents independently selected from
  • Preferred compounds A are compounds of Formula I wherein: A is A-1;
  • Q is selected from the group J, Cj-C j g alkyl and C 2 -C j g alkenyl; and J is selected from the group phenyl and thienyl, each optionally substituted with 1-3 substituents independently selected from the group R 3 .
  • Preferred Compounds B are Compounds of Preferred A wherein: Q is J; and
  • Preferred Compounds C are Compounds B wherein: G 1 is C(O); R 1 is selected from the group F and Cl in the 2-position;
  • R 2 is selected from the group H, F and Cl in the 6-position;
  • R 3 is independently selected from the group, halogen, C j -Cg alkyl, C j -C 6 haloalkyl, OR 20 and M-J 1 ;
  • R 20 is selected from the group C J -C 4 alkyl and CJ-C4 haloalkyl;
  • J 1 is selected from the group phenyl, thienyl, pyridyl and furyl.
  • Compound D of Preferred C which is: N-[2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolyl]-2-fluoro-4-(trifluoro- methyl)benzamide.
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when anriched relative to the other stereoisomer(s) or when seperated from the other stereoisomer(s).
  • the skilled artisan knows how to separate said stereoisomers. Accordingly, the present invention comprises racemic mixtures, individual stereoisomers, and optically active mixtures of compounds of Formula I as well as agriculturally suitable salts thereof.
  • aromatic ring and "aromatic ring system” are defined as those rings or ring systems which satisfy the H ⁇ ckel rule. Examples include: a 5- or 6- membered monocyclic aromatic ring containing 0 to 4 heteroatoms such as phenyl, furyl, furazanyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, oxadiazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl isothiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl with said ring attached through any available carbon or nitrogen.
  • the aromatic ring system is furyl, it can be 2-furyl or 3-furyl, for pyrrolyl, the aromatic ring system is 1 -pyrrolyl, 2-pyrrolyl or
  • 3-pyrrolyl for pyridyl, the aromatic ring system is 2-pyridyl, 3-pyridyl or 4-pyridyl and similarly for other monocyclic aromatic rings; fused carbobicyclic rings containing at least one phenyl ring, examples include naphthyl and tetralinyl; fused carbotricyclic ring containing at least one phenyl ring, examples include fluorenyl and phenanthrenyl; fused bicyclic rings containing 1 to 4 heteroatoms and 1 or 2 aromatic rings, examples include quinolyl, isoquinolyl, quinoxalinyl, benzofuryl, isobenzofuranyl, benzothienyl, benzodioxolyl, chromanyl, indolinyl, isoindolyl, thienofuranyl, and purinyl; and fused tricyclic rings containing 1 to 6 heteroatoms and at least 1 aromatic ring, examples include acri
  • the bicyclic and tricyclic aromatic ring systems can be attached through any available carbon or nitrogen, for example, for naphthyl, the carbobicyclic aromatic ring system is 1 -naphthyl or 2-naphthyl, for benzofuryl, the aromatic ring system can be 2-, 3-, 4-, 5-, 6-, or 7-benzofuryl, for fluorenyl, the aromatic ring system can be 1-, 2-, 3-, 4-, or 9-fluorenyl and similarly for the other bicyclic and tricyclic aromatic ring systems.
  • alkyl used either alone or in compound words such as
  • alkylthio or haloalkyl denotes straight-chain or branched alkyl, such as, methyl, ethyl, ⁇ -propyl, i-propyl, or the different isomers through Cjg.
  • alkylene examples include CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 and the different butylene isomers.
  • Alkenyl denotes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different isomers through C j g.
  • Alkenyl also denotes polyenes such as 1,3-hexadiene.
  • Alkynyl denotes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 3-propynyl and the different isomers through C j g.
  • alkynylene examples include C ⁇ C, CH 2 C ⁇ C, G ⁇ CCH2 and the different butynylene isomers.
  • Alkoxy denotes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl examples include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH3CH2CH2CH2OCH2 and CH 3 CH 2 OCH2CH 2 and the different isomers through C j g.
  • Alkylthio denotes straight-chain or branched alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl.
  • Alkylthioalkyl examples include CH 3 SCH 2 . CH 3 CH 2 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 CH 2 SCH 2 , CH3CH2SCH2CH2 and the different isomers through C 16 .
  • Alkylsulfonyl denotes CH 3 S(O) 2 and CH 3 CH 2 S(O) 2 .
  • Cycloalkyl denotes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • cycloalkylalkyl examples include cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl and the different Cg and C7 isomers bonded to straight-chain or branched alkyl groups.
  • Alkoxycarbonylalkyl denotes straight-chain or branched esters substituted on straight-chain or branched alkyl groups.
  • alkoxycarbonylalkyl examples include CH 2 C(O)OCH3, CH 2 C(O)OCH 2 CH 3 , CH 2 CH 2 C(O)OCH 3 and the different isomers through C 18 .
  • halogen either alone or in compound words such as “haloalkyl”, denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkynyl examples include HC ⁇ CCHCl, CF 3 C ⁇ C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, CF 2 HCH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CC1 3 S, CF 3 S, and CC1 3 CH 2 S.
  • haloalkylsulfonyl examples include CF 3 SO 2 , CCI3SO2, CF3CH2SO2 and CF3CF2SO2.
  • Cj-C j The total number of carbon atoms in a substituent group is indicated by the "Cj-C j " prefix where i and j are numbers from 1 to 18.
  • Cj-Cg alkyl designates methyl, ethyl, and propyl through hexyl isomers
  • C 2 alkoxy designates CH 3 CH 2 O-
  • C 3 alkoxy designates CH 3 CH 2 CH 2 O- or (CH 3 ) 2 CHO-.
  • Nitroalkyl designates a straight or branched-chain alkyl group substituted with NO2.
  • Cyanoalkyl designates a straight or branched-chain alkyl group substituted with CN.
  • a generally useful method is the reaction of the Formula II compound with the Formula III compound in the presence of an acid scavenger (usually a tertiary amine base such as triethylamine) at room temperature or below.
  • the reaction can be carried out in an inert solvent such as methylene chloride, tetrahydrofuran, chloroform, toluene and other solvents that will not react with acid chlorides or bases.
  • the reaction is normally completed in less than 24 h.
  • Other useful methods for the formation of amides, sulfonamides and carbamates are discussed in Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York.
  • G 1 C(0), S(0)2 or C(0)0.
  • Typical reactions involve the combination of equimolar amounts of II and IV in an organic solvent such as ethyl acetate, methylene chloride, tetrahydrofuran, chloroform, benzene or toluene.
  • a base such as an alkali metal, tertiary amine, alkali metal hydroxide or metal hydride can be used.
  • the reaction can be run at temperatures ranging from about -20-100 °C with temperatures in the range of -10-30 °C being preferred. The reaction is completed within
  • Compounds of Formula I (where A is A-l and Y is H) can be prepared by reaction of a compound of Formula II with an aldehyde of Formula V as shown in Scheme 3. This reaction can be carried out in a solvent such as methanol or ethanol in the presence of a reducing agent such as sodium borohydride or sodium cyanoborohydride (Borch et al., J. Am. Chem. Soc. (1971), 93, 2897). The reaction temperature can vary from -30-200 °C and the reaction is completed in about 2-72 h.
  • Scheme 3
  • Formula I compounds (where A is A-l, A-l is QCH 2 N(Y) and Y is H) can be prepared by the reduction of compounds of Formula I (where A is A-l, A-l is QC(O)N(Y) and Y is H) as shown in Scheme 4.
  • Useful reducing agents are alkali metal hydrides.
  • treatment of a compound of Formula I (A is A- 1 , G 1 is C(O) and Y is H) with lithium aluminum hydride at 0-50 °C in ethereal solvents such as tetrahydrofuran, ether or dimethoxyethane yields compounds of Formula I (A is A-l and Y is H).
  • the reduction is usually completed in 24 h.
  • Compounds of Formula II can be prepared by the reaction of compounds of Formula VI with sodium hypobromite (or sodium hydroxide and bromine). This transformation is shown in Scheme 5. A review of the Hofmann rearrangement can be found in Org. Rxns. (1946), 3, pp. 267-306.
  • a typical reaction involves the addition of a compound of Formula VI to an aqueous solution of sodium hypobromite.
  • the temperature of the reaction can range from 0-200 °C with the preferred temperature range between 30-100 °C.
  • the reaction is usually complete in 24 h.
  • the transformation can be accomplished by treating a
  • Compounds of Formula VI can be prepared by reacting compounds of Formula VII with ammonia. This transformation is shown in Scheme 6. The reaction can be run in solvents such as methanol, ethanol, ether, benzene and toluene. Typical reactions are carried out at ambient temperature, and reactions are usually completed in 24 h. For reference, see D. W. Jones, J. Chem. Soc. (1969), 1729.
  • Compounds of Formula VII can be prepared by the reaction of commercially available serine derivatives (Formula VIII) with an imidate of Formula IX as shown in Scheme 7.
  • the reaction can be carried out in solvents such as methanol, methylene chloride, chloroform, benzene, dioxane and tetrahydrofuran. Water can be added as a cosolvent.
  • imidates of Formula IX can be prepared from commercially available amides of Formula X by reaction with a trialkyloxonium tetrafluoroborate in an inert solvent such as methylene chloride, benzene or toluene.
  • an inert solvent such as methylene chloride, benzene or toluene.
  • an appropriate halogenating agent such as phosphorous trichloride, phosphorous tribromide, phosphorous pentachloride, phosphorous pentabromide, thionyl chloride, thionyl bromide, sulfuryl chloride, triphenylphosphorous and carbon tetrachloride or carbon t
  • Typical reactions involve combination of the reactant with an excess of halogenating agent in the presence or absence of an organic solvent such as benzene, toluene, xylene, chloroform, methylene chloride and hexane.
  • an organic solvent such as benzene, toluene, xylene, chloroform, methylene chloride and hexane.
  • the preferred reaction temperature ranges from 35-100 °C and the reaction is generally complete within 24 h.
  • Compounds of Formula I can be prepared by reaction of Formula II compounds with Formula V compounds.
  • Typical reactions include the combination of equimolar amounts of Formula II compounds with Formula V compound in a suitable solvent such as acetonitrile, methanol, ethanol or benzene.
  • the reaction can be run in the presence or absence of an acid catalyst.
  • Typical acid catalysts include alkyl or arylsulfonic acids and mineral acids such as hydrochloric acid.
  • the reaction temperature can vary from 0 °C to the reflux temperature of the particular solvent being used. Scheme 11 illustrates this transformation. The reaction is normally completed within 24 h.
  • Compounds of Formula I (where A is A-2, G 2 is O, S or NH and X 1 is O) can be prepared by condensation of Formula XI compounds with Formula XII compounds.
  • a generally useful method is treatment of an acid chloride of Formula XI with an amine, alcohol or thiol of Formula XII in the presence of an acid scavenger such as triethylamine at room temperature or below.
  • the reaction can be carried out in an inert solvent such as methylene chloride, tetrahydrofuran, toluene, benzene and chloroform.
  • An alternative method is treatment of an acid of Formula XI with a Formula XII compound in the presence of a condensation reagent such as dicyclohexylcarbodiimide in a suitable solvent such as methylene chloride, chloroform, tetrahydrofuran, toluene, dimethylformamide and ethyl acetate.
  • a condensation reagent such as dicyclohexylcarbodiimide
  • a suitable solvent such as methylene chloride, chloroform, tetrahydrofuran, toluene, dimethylformamide and ethyl acetate.
  • the temperature can range from 0-200 °C with the preferred temperature range from 20-100 °C.
  • the reaction can be run in the presence of a catalyst such as dimethylaminopyridine (see Synthesis (1972), 453) and is completed in 30 min to 48 h.
  • Compounds of Formula XI can be prepared by hydrolysis of a Formula VII compound as shown in Scheme 13. Typical reactions involve treating Formula VII compounds with a base such as sodium hydroxide or potassium hydroxide in a suitable solvent such as water, methanol or ethanol. The reaction temperature can vary from 0 °C to the reflux temperature of the particular solvent being used. Hydrolysis of esters have been thoroughly discussed in March, Advanced Organic Chemistry, 3rd Ed., (1985), pp 334-338. Typical reactions are completed in less than 24 h.
  • Compounds of Formula I can be prepared by reaction of compounds of Formula XIII with an aldehyde of Formula V in the presence of a strong base. This transformation is shown in Scheme 14.
  • a typical reaction involves mixing a compound of Formula XUI with a strong base such as an alkyllithium (e.g., butyllithium), a metal alkoxide (e.g., sodium methoxide), sodium amide or sodium hydride in a suitable solvent such as tetrahydrofuran, ether, benzene, methanol, ethanol, toluene, dimethoxyethane and dimethylsulfoxide, followed by the addition of an aldehyde of Formula V.
  • the temperature of the reaction can vary from -70-200 °C.
  • the Wittig reaction has been reviewed by Maercker in Org. Rxns. (1965), 14, pp 270-490. The reaction is complete in 1-48 h.
  • Formula XIII compounds can be prepared by reaction of equimolar amounts of a Formula XIV compound and triphenylphosphine. The transformation is shown in Scheme 15.
  • the reaction can be run in a solvent such as benzene, toluene, xylene, ether, tetrahydrofuran, nitromethane, nitrobenzene, acetonitrile, ethyl acetate and dimethylformamide.
  • the reaction temperature can vary from 0-200°C. For details see Maercker, Org. Rxn. (1965), 14, pp 270-490.
  • the reaction is completed in 24 h.
  • the reaction involves combination of an alcohol of Formula XV with a halogenating agent such as triphenylphosphine and carbon tetrachloride or carbon tetrabromide, triphenylphosphine, imidazole and iodine in a suitable solvent such as acetonitrile or methylene chloride.
  • a halogenating agent such as triphenylphosphine and carbon tetrachloride or carbon tetrabromide
  • triphenylphosphine imidazole and iodine
  • a suitable solvent such as acetonitrile or methylene chloride.
  • Compounds of Formula I (where A is A-6, G 6 is C 2 alkylene, and Q is aryl) can be prepared by reaction of a compound of Formula XVI, first with thionyl chloride and then with sodium hydroxide in methanol as shown in Scheme 18.
  • a typical reaction involves mixing a compound of Formula XVI with thionyl chloride neat or with a suitable solvent such as toluene or carbon tetrachloride. The mixture is heated from 30-100°C for 0.25-4 h. The solvent and excess thionyl chloride are concentrated under vacuum and the resultant crude chloride is dissolved in methanol and treated with aqueous sodium hydroxide. This second reaction is then heated for 0.25-4 h at 30-65°C. Extraction of the cooled reaction mixture with an organic solvent enables the isolation of the product of Formula I where A is A-6 and G 6 is C 2 alkylene.
  • Compounds of Formula XVI can be prepared from compounds of Formula XVII as shown in Scheme 19.
  • Amino alcohols of Formula XVII are first converted to silyl ethers by reaction with trimethylsilyl cyanide at 0-30°C in a suitable solvent such as methylene chloride, chloroform, or tetrahydrofuran.
  • a suitable solvent such as methylene chloride, chloroform, or tetrahydrofuran.
  • the alcohol group in compounds of Formula XVII is protected as the silyl ether so it does not react with the benzoyl chloride in the next step.
  • the solution of silyl ether is treated with an organic base like triethylamine and then with an appropriate benzoyl chloride at 0-30°C for 0.5-4 h.
  • the crude intermediate amide can be isolated by addition of water and extraction with an appropriate organic solvent.
  • the silyl ether protecting group is removed by treatment of the crude intermediate (dissolved in an appropriate solvent like tetrahydrofuran) with a solution of tetrabutylammonium fluoride at 0-30°C for 5-60 min.
  • Compounds of Formula XVI are then isolated by addition of water and extraction with an organic solvent like ethyl acetate.
  • Compounds of Formula XVIII can in turn be prepared from compounds of Formula XIX as shown in Scheme 21.
  • An epoxide of Formula XIX is dissolved in an appropriate solvent like tetrahydrofuran and treated with one equivalent of phthalimide and a catalytic amount (10 mol %) of an appropriate palladium catalyst like tetrakis-(triphenylphosphine) palladium (0) at 15-35°C for 0.5-4 h.
  • Compounds of Formula I (where R 1 and R 2 are halogens and R 3 is alkyl or aryl) can be obtained by reaction of a compound of Formula XXII with a base.
  • Compounds of Formula XXII are prepared by reacting substituted benzamide with 2-haloacetaldehyde dialkylacetal (see EP-A-594J29). The conversion of XXII to I takes place at room temperature over a period of several hours. Scheme 24 discloses this transformation.
  • Step D 2-(2.6-Difluorophenyl -4,5-dihydro-N-f4-methoxyphenyl)-4- oxazolecarboxamide
  • the compound, 1 ,3-dicyclohexylcarbodiimide (0.433 g, 0.0021 mol) was added to a mixture of the product of Step C (0.500 g, 0.0021 mol), 4-dimethylaminopyridine (0.044 g, 0.00036 mol) and p-anisidine (0.259 g, 0.0021 mol) in 3.5 mL of methylene chloride. The mixture was stirred at reflux for 1.5 h.
  • Step B 2-(2.6-Difluorophenyl)-4.5-dihydro-4-oxazolamine An amount of 0.386 g (0.0044 mol) of bromine was added dropwise to a cooled solution of 0.440 g (0.011 mol) of ⁇ aOH in 3.7 mL of H 2 O. 0.500 g (0.002 mol) of the product of Step A was added portionwise. The reaction was stirred at 80 °C for 0.5 h. Et 2 O and H O was added and the mixture extracted with EtOAc. The combined extracts were washed with brine, dried MgSO 4 and evaporated to give 0.350 g of a white solid: m.p.
  • Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent.
  • Useful formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation.
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 weight percent.
  • Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill.
  • Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., (1988), pp 251-259.
  • Suspensions are prepared by wet-milling; see, for example, U.S. 3,060,084.
  • Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques.
  • Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • Example D Emulsifiable Concentrate
  • Compound 1 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%.
  • the compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term “arthropods” includes insects, mites and nematodes) which are pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the art will appreciate that not all compounds are equally effective against all growth stages of all pests.
  • compounds of this invention display activity against one or more of the following pests: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs, immatures and adults of the Orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eggs, immatures and adults of the Orders Thysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, junveniles and adults of the Phylum Nematoda.
  • the compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes.
  • the compounds are active against southern corn rootworm (Diabrotica undecimpunctata howardi), aster leafhopper (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite ⁇ Tetranychus urticae), fall armyworm (Spodoptera frugiperda), black bean aphid (Aphis fabae), green peach aphid (Myzus persica), cotton aphid (Aphis gossypii), Russian wheat aphid (Diuraphis noxia), English grain aphid (Sitobion avenae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatella furcifera), green leafhopper (Nephotettix cincticeps), brown planthopper
  • Tetranychidae including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonychus citri, Eotetranychus carpini borealis, Eotetranychus, hicoriae, Eotetranychus sexmaculatus, Eotetranychus yumensis, Eotetranychus banksi and Oligonychus pratensis; Tenuipalpidae including Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus californicus and Brevipalpus obovatus; Eriophyida
  • Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellants, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • insecticides such as avermectin B, monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, metha-midophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, t
  • Arthropod pests are controlled and protection of agronomic, horticultural and specialty crops, animal and human health is achieved by applying one or more of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • the present invention further comprises a method for the control of foliar and soil inhabiting arthropods and nematode pests and protection of agronomic and/or nonagronomic crops, comprising applying one or more of the compounds of Formula I, or compositions containing at least one such compound, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • a preferred method of application is by spraying.
  • granular formulations of these compounds can be applied to the plant foliage or the soil.
  • Other methods of application include direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others.
  • the compounds can be inco ⁇ orated into baits that are consumed by the arthropods or in devices such as traps and the like.
  • the compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use.
  • a preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, and synergists and other solvents such as piperonyl butoxide often enhance compound efficacy.
  • the rate of application required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.001 kg/hectare may be sufficient or as much as 8 kg hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required.
  • Control efficacy represents inhibition of arthropod development (including mortality) that causes significantly reduced feeding.
  • Test units each consisting of a 230 mL (8 ounce) plastic cup containing a 2.54 cm 2 plug (1 square inch) of a wheatgerm diet, were prepared. Solutions of each of the test compounds in 75/25 acetone/distilled water solvent were sprayed into the tray and cup. Spraying was accomplished by passing the tray and cup on a conveyer belt directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.55 kg of active ingredient per hectare (about 0.5 pounds per acre) at 207 kPa (30 p.s.i.). After the spray on the cups had dried, five second- instar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardi) were placed into each cup. The cups were held at 27°C and 50% relative humidity for 6-8 days. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 54.
  • Pieces of kidney bean leaves each approximately 2.54 cm 2 (1 square inch) in area, that had been infested on the undersides with 25 to 30 adult mites (Tetranychus urticae), were sprayed with their undersides facing up on a hydraulic sprayer with a solution of the test compound in 75/25 acetone/distilled water solvent. Spraying was accomplished by passing the leaves, on a conveyor belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.55 kilograms of active ingredient per hectare (about 0.5 pounds per acre) at 207kPa (30 p.s.i.).
  • the leaf squares were then placed underside-up on square of wet cotton in a petri dish and the perimeter of the leaf square was tamped down onto the cotton with forceps so that the mites could not escape onto the untreated leaf surface.
  • the test units were held at 27°C and 50% relative humidity for 7 days and read for larvacide/ovacide mortality Of the compounds tested, the following gave activity levels of 80% or higher: 5, 7, 12, 13, 19, 20 and 27.
  • test compound was prepared by dissolving it in a minimum of acetone and then adding water containing a wetting agent until the concentration of the compound was 100 ppm.
  • Two- week old red kidney bean plants infested with two-spotted spider mite eggs (Tetranychus urticae)wcre. sprayed to run-off with the test solution using a turntable sprayer. Plants were held in a chamber at 25°C and 50% relative humidity and scored for activity seven days after spray.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
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  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Abstract

Cette invention concerne des composés et des compositions arthropodicides et des procédés d'utilisation de composés de formule (I) dans laquelle A, E, Z, R1, R2 et Q sont tels que définis dans le texte.
EP95908447A 1994-01-24 1995-01-17 2-oxa et thia-zolines arthropodicides Withdrawn EP0741714A1 (fr)

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US18555094A 1994-01-24 1994-01-24
US185550 1994-01-24
PCT/US1995/000208 WO1995019972A1 (fr) 1994-01-24 1995-01-17 2-oxa et thia-zolines arthropodicides

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AU2002305669B2 (en) * 2001-05-21 2008-09-11 E.I. Du Pont De Nemours And Company Diamide invertebrate pest control agents containing a non-aromatic heterocyclic ring
US7273866B2 (en) 2002-12-20 2007-09-25 Bristol-Myers Squibb Company 2-aryl thiazole derivatives as KCNQ modulators
US6933308B2 (en) 2002-12-20 2005-08-23 Bristol-Myers Squibb Company Aminoalkyl thiazole derivatives as KCNQ modulators
CA2528764A1 (fr) * 2003-06-13 2004-12-29 Janssen Pharmaceutica N.V. Derives de thiazoline servant de modulateurs de recepteur des androgenes selectifs (sarms)
JP2023007504A (ja) * 2019-09-30 2023-01-19 日本農薬株式会社 イミン化合物またはその塩、および該化合物を有効成分として含有する有害生物防除剤並びに有害生物防除方法
CN115894398B (zh) * 2022-12-02 2024-03-12 青岛科技大学 一种含氟噻唑酰胺类杀虫杀螨剂

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US4977171A (en) * 1988-06-09 1990-12-11 Yashima Chemical Industrial Co., Ltd. Oxa- or thia-zoline derivative
AU634608B2 (en) * 1989-12-09 1993-02-25 Kyoyu Agri Co., Ltd. 2-substituted phenyl-2-oxazoline or thiazoline derivatives, process for producing the same and insectides and acaricides containing the same
EP0646111B1 (fr) * 1992-05-26 1997-08-20 E.I. Du Pont De Nemours And Company Oxazolines et thiazolines pour la destruction des arthropodes

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AU1676595A (en) 1995-08-08
NZ279591A (en) 1997-04-24

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