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WO2001068589A1 - Composes acrylonitrile et agents pesticides - Google Patents

Composes acrylonitrile et agents pesticides Download PDF

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Publication number
WO2001068589A1
WO2001068589A1 PCT/JP2001/002096 JP0102096W WO0168589A1 WO 2001068589 A1 WO2001068589 A1 WO 2001068589A1 JP 0102096 W JP0102096 W JP 0102096W WO 0168589 A1 WO0168589 A1 WO 0168589A1
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Prior art keywords
group
alkyl group
alkoxy
substituted
alkyl
Prior art date
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PCT/JP2001/002096
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English (en)
Japanese (ja)
Inventor
Tomio Yagihara
Yasushi Shibata
Tatsumi Suzuki
Shigemi Suga
Minoru Sakatani
Renpei Hatano
Takao Iwasa
Tomohiro Take
Yukuo Mukohara
Yoshinobu Fujii
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Nippon Soda Co Ltd
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Nippon Soda Co Ltd
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Priority to AU2001241170A priority Critical patent/AU2001241170A1/en
Publication of WO2001068589A1 publication Critical patent/WO2001068589A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • 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
    • A01N47/02—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 no bond to a nitrogen atom
    • A01N47/06—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 no bond to a nitrogen atom containing —O—CO—O— groups; 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
    • 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
    • A01N47/12—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, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/37—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by etherified hydroxy groups
    • 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
    • C07D277/22—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to a novel nitrile derivative of thiazolyl cinnamate and a pesticidal agent containing the derivative as an active ingredient.
  • citrate nitrile derivatives similar to the compounds of the present invention include, for example, JP-A-53-92769, JP-A-55-154963, and EP189890.
  • An object of the present invention is to provide a pesticidal agent comprising a ditolyl thiazolyl cinnamate derivative as an active ingredient, which is effective and can be used safely.
  • the present invention relates to the following (a) —general formula (1)
  • A5 A6 (Wherein, it represents a halogen atom, an alkyl group, C i 6 haloalkyl group, - 6 alkoxy group, an optionally substituted C 3 _ 6 cycloalkyl group, in optionally substituted pyridyl group, in substitution A phenyl group which may be substituted with a phenyl group or a phenyl group which may be substituted with
  • X 2 is a hydrogen atom, a halogen atom, CI- e alkyl group, C i-6 haloalkyl group, C, _ 6 alkoxy Cal Poni group, a C 3 6 cycloalkyl group or an optionally substituted phenylene Le group Wi Represent
  • X 3 and X 4 are each independently a hydrogen atom, a halogen atom, an alkyl group,
  • C i—e represents an alkoxyl group
  • X 5 represents a hydrogen atom, a C ⁇ e alkyl group, a C i-6 cycloalkyl group, a Ci 6 haloalkyl group, a C i 6 alkoxy C 6 alkyl group,
  • X 6 is a hydrogen atom, a halogen atom, a C 6 alkyl group, a C 3 _ 6 cycloalkyl group, a C 6 haloalkyl group, a d 6 alkoxy group, a C 6 alkoxy C i 6 alkyl group, a C 6 alkoxycarbonyl. Represents a phenyl group which may be substituted with
  • X 7 is substituted with a nitro group, a cyano group, a halogen atom, a C—e alkyl group, a C— 6 cycloalkyl group, a —6 haloalkyl group, a —6 alkoxy group, a C i- 6 haloalkoxy group, A phenyl group, a pyridyl group optionally substituted with, a phenyl group optionally substituted with, a pyridyloxy group optionally substituted with
  • n 0 or an integer of 1 to 5.
  • W 2 is substituted with substituted also a good phenyl group or W 2 represents a heterocyclic group which may,
  • W 2 is Shiano group, a nitro group, a halogen atom, Ji 6 alkyl group, flicking 6 Haroaru kill group, C i 6 alkoxy group, C 6 haloalkoxy group, C 3 8 cycloalkyl group, which may have a substituent It represents a good phenyl group or a phenoxy group which may have a substituent, and W 2 may be the same or different and may be plurally substituted.
  • the heterocyclic group which may be substituted with 2 is triazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, chenyl, furyl, pyrrolyl, pyridyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl It is a kind of group selected from the group.
  • R is an alkyl group, a haloalkyl group, flicking 6 alkoxy groups, 6 ⁇ alkoxy C 6 alkyl group, d 6 alkylthio group, C] 6 alkylthio C Al kill group, mono C i 6 alkylamino group, current events ⁇ - 6 alkyl amino group, an optionally substituted C 3 _ 6 consequent opening alkyl group, an optionally substituted phenyl C alkyl group, an optionally substituted phenoxy C i _ 6 alkyl group, a substituted A phenylthio C i_ 6 alkyl group which may have a group or a phenyl group which may have a substituent,
  • Cie alkyl group Represents a nitrogen atom
  • Y 2 represents an oxygen atom or a sulfur atom
  • a pesticidal composition characterized by containing one or more of the acrylonitrile compounds as an active ingredient.
  • the present invention is an industrially advantageous method for producing the compound represented by the general formula (2), which is an intermediate for producing the compound of the present invention.
  • halogen atoms such as fluorine, chlorine, bromine and iodine, methyl, ethyl, butyl, isopropyl, butyl, sec-butyl, isoptyl, t-butyl, pentyl and its isomers, hexyl and its isomers
  • X 2 is a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine, or iodine, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and C alkyl groups such as isomers, chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tripromomethyl, 2,2,2-trichloroethyl, 2,2, 2-triflate Ruo Roe chill, such as penta full O Roe Chi le C - 6 eight-necked alkyl group, main Bok alkoxycarbonyl, ethoxycarbonyl, Provo alkoxycarbonyl, Isopurobokishi, butoxycarbonyl, t-butoxide deer Lupo
  • X 3 and X 4 are a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine, or iodine, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and isomers thereof.
  • C- 6 alkyl groups such as xyl and its isomers, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopoxy
  • X 5 represents a hydrogen atom, a C- 6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isoptyl, t-butyl, pentyl and its isomers, hexyl and its isomers, cyclopropyl, It represents a 6 alkoxy C i _ 6 alkyl group - cyclopentyl, C 3 _ 6 cycloalkyl group such as cyclohexyl, main Tokishimechiru, main Tokishechiru, ethoxymethyl, Provo carboxymethyl, C i of butoxymethyl and the like.
  • X 6 is a hydrogen atom, a halogen atom such as fluorine, chlorine, bromine, or iodine, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and the like.
  • C i _ 6 alkyl groups such as isomers, cyclo propyl, cyclopentyl, C 3, such as cyclohexyl - 6 cycloalkyl group, click port Romechiru, Furuoromechiru, bromomethyl, dichloromethyl, Jifuruoromechiru, dibromomethyl, trichloromethyl, triflic C— 6 haloalkyl groups such as chloromethyl, tripromoxymethyl, 2,2,2_trichloroethyl, 2,2,2-trifluoroethyl, pendufluorethyl, methoxy, ethoxy, propoxy, isopropoxy, Butoxy, sec — butoxy, isobutoxy, t — C—e alkoxy groups such as butoxy, C— 6 alkoxy C—6 alkyl groups such as methoxymethyl, methoxyshetyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxycarbonyl, eth
  • X 7 is a halogen atom such as a cyano group, a nitro group, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and C i, such as their isomers - e alkyl group, cyclopropyl, cyclopentyl, C 3 _ 6 cycloalkyl group such as cyclohexyl, chloromethyl, Furuoromechiru, Promo methyl, dichloromethyl, Jifuruoromechiru, diblock ⁇ , trichloromethyl, Ci- 6 haloalkyl groups such as trifluoromethyl, tripromomethyl, 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl and pentafluoroethyl, methoxy, ethoxy,
  • X 7 may be the same or different.
  • halogen atoms such as cyano group, nitro group, fluorine, chlorine, and bromine; methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and its isomers 6 cycloalkyl group, - C such body, _ 6 alkyl groups, cyclopropyl, cyclopentyl, C 3, such as cyclohexyl Chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tripromethyl, 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl, pen Ci— 6 haloalkyl groups such as fluorethyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec—butoxy
  • W 2 is substituted with substituted also a good phenyl group or W 2 represents a heterocyclic group which may,
  • W 2 is a halogen atom such as a cyano group, a nitro group, fluorine, chlorine, and bromine; methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and isomers thereof, hexyl and C alkyl group such as its isomer, chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tripromomethyl, 2,2,2-trichloroethyl, 2,2, 2—C- 6 haloalkyl groups such as trifluoroethyl and pentafluoroethyl, d- 6 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec—butoxy, isobutoxy, t—butoxy , Chloromethoxy
  • the heterocyclic group in the heterocyclic group which may be substituted by W 2 includes 1,2,3-triazolyl, 1,2,4-triazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, virazolyl, imidazolyl, tetrazolyl, 2,3-oxadiazolyl, 1,2,4—oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, chenyl , .Furyl, pyrrolyl, pyridyl, pyridazinyl, pyrimidinyl, birazinyl.
  • R is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and its isomers, heptyl and its isomers, Noel and its isomers,
  • a d- 12 alkyl group such as dodecyl and its isomer, particularly a branched alkyl group, is preferred.
  • 2 1 and 2 are each independently a hydrogen atom or a C 6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isoptyl, t-butyl, chloromethyl, fluoromethyl, bromomethyl, Cie octaalkyl such as dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl and pentafluoroethyl C- 6 alkoxy C alkyl groups such as methoxymethyl, methoxethyl, propoxymethyl, and butoxymethyl; C- 6 alkylthio C i such as methylthiomethyl, methylthioethyl, ethylthioethyl, ethylthiomethyl, propylthiomethyl, and but
  • the production method of the present invention is represented by the following reaction formula.
  • the present invention compound represented by the general formula (1) can be obtained by reacting 0.5 to 2 mol of the compound represented by the formula (3) in the presence of an inert solvent.
  • solvent used in this reaction examples include polar solvents such as N, N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), ether solvents such as tetrahydrofuran (THF), ketone solvents such as acetone, Examples include nitrile solvents such as acetonitrile, chlorinated solvents such as dichloromethane, chloroform, carbon tetrachloride, hexamethyl phosphate amide (HMPA), benzene, and toluene.
  • polar solvents such as N, N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO)
  • ether solvents such as tetrahydrofuran (THF)
  • ketone solvents such as acetone
  • nitrile solvents such as acetonitrile
  • chlorinated solvents such as dichloromethane, chloroform, carbon tetrachloride, hexamethyl phosphate
  • bases examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, metal hydrides such as sodium hydride, n-butyllithium, lithium diisopropyl
  • bases include organic metals such as amides (LDA) and organic bases such as triethylamine, diisopropylethylamine and pyridine.
  • bases are used in the best combination at the time of use by selecting a substrate, a solvent, and the like.
  • a compound in which L in the general formula (3) is chlorine or bromine It is effective to carry out the reaction in the presence of sodium iodide and potassium iodide in the presence of sodium iodide and usually in equimolar amounts with (3).
  • the reaction temperature is preferably from room temperature to the boiling point of the solvent used, and the reaction time is in the range of 1 hour to 48 hours.
  • the desired product can be obtained by performing ordinary post-treatment.
  • the structure of the compound of the present invention was determined from IR, NMR and MS.
  • the compound of the present invention represented by the general formula (1) has two types of stereoisomers, and depending on the reaction conditions and purification method, either one of the isomers may be obtained or the mixture of isomers may be used. May be obtained. All of these isomers are included in the scope of the present invention.
  • the method for producing the compound represented by the formula (2) as a production raw material is described in the above cited document.
  • the compound in which ⁇ is AI can be obtained as follows.
  • Q is a halogen atom, C i_ e alkoxy group, phenoxy group, a leaving group such as I imidazolyl group or I pyrazolyl group.
  • the cited documents include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, organic metals such as n-butyl lithium and LDA, and triethylamine. And organic bases such as diisopropylethylamine, pyridine, and the like. Production examples using sodium hydride are described, but they cannot be said to be industrially advantageous.
  • the present inventors have made the compound represented by the general formula (4) into a magnesium salt using a magnesium alkoxide or the like, and then reacted with the compound represented by the general formula (5), thereby mildly. It has been found that the desired product can be obtained in a high yield under suitable conditions.
  • an aromatic hydrocarbon solvent such as benzene and toluene can be used.
  • the reaction temperature is preferably in the temperature range from room temperature to the boiling point of the solvent used. Representative examples of the compounds of the present invention that can be produced as described above are shown in Tables 2 to 6. The abbreviations in the table have the following meanings.
  • Table 1 shows specific examples of the partial structure G of the general formula (1).
  • composition containing the compound of the present invention obtained in this way is useful, for example, as an insecticide, a pesticide, a sanitary pest control agent, or an antifouling agent for water-borne organisms.
  • the composition containing the compound of the present invention can be particularly preferably applied as an insecticide or acaricide.
  • the compound of the present invention when it is actually applied as an insecticide or acaricide, it can be used in a pure form without adding other components, and can be in the form of a general pesticide for use as a pesticide, for example, It can also be used in the form of wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, flowables, wettable powders and the like.
  • additives and carriers include soybean grains, vegetable powders such as flour, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay and other mineral powders.
  • Organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate can be used.
  • kerosene, xylene and petroleum aromatic hydrocarbons, cyclohexane, cyclohexanone, DMF, DMSO, alcohol, acetone, trichloroethylene, methyl are used as additives and carriers.
  • Isobutyl ketone, mineral oil, vegetable oil, water, etc. can be used as the solvent.
  • a surfactant may be further added, if desired.
  • the surfactant is not particularly limited.
  • alkyl phenyl ether to which polyoxyethylene is added alkyl ether to which polyoxyethylene is added, higher fatty acid ester to which polyoxyethylene is added, sorbitan to which polyoxyethylene is added
  • Nonionic surfactants such as higher fatty acid esters, tristyryl ether to which polyoxyethylene has been added, sulfates of alkylphenyl ethers to which polyoxyethylene has been added, alkylbenzene sulfonates, sulfuric acid of higher alcohols
  • Examples thereof include ester salts, alkyl naphthalene sulfonates, polycarboxylic acid salts, lignin sulfonates, formaldehyde condensates of alkyl naphthylene sulfonates, and copolymers of isobutylene monomaleic an
  • the amount of the active ingredient (compound of the present invention) in the preparation is preferably about 0.01 to 90% by weight, more preferably about 0.05 to 85% by weight.
  • the obtained wettable powder, emulsion, suspension, flowable, aqueous solvent, and granular wettable powder are diluted with water to a specified concentration to obtain a solution, suspension, or emulsion, which is used as a powder, granule, etc.
  • the agent is used by spraying it on plants or soil as it is.
  • the formulated pesticidal composition of the present invention is applied to a plant, a seed, a water surface or soil as it is or after being diluted with water or the like.
  • the application rate varies depending on the weather conditions, formulation, application magnetism, application method, application site, target disease, target crop, etc., but usually 1 to 1 to 1,000 g in terms of the amount of active compound per quartal. And preferably 100 to 100 g.
  • the application concentration is 1 to 100 ppm, preferably 100 to 2 ppm. 50 ppm. In the case of granules and powders, apply directly without dilution.
  • the compound of the present invention alone is sufficiently effective, but it can also be used in combination with one or more of various fungicides, insecticides and acaricides, or synergists.
  • Representative examples of fungicides, insecticides, acaricides, and plant growth regulators that can be used by mixing with the compound of the present invention are shown below.
  • Plant growth regulator Plant growth regulator
  • Gibberellins eg, gibberellin A 3, gibberellin A 4, gibberellin A 7
  • IA A, N A A and the like The compound of the present invention can be used for controlling agricultural pests, sanitary pests, storage pests, clothing pests, house pests, and the like, and has an insecticidal, nymphalidal, larvicidal, and ovicidal action.
  • the following are typical examples.
  • Lepidopteran insect pests for example, Spodoptera litura, Ganoderma elegans, Managana evening, Aomushi, Managinaba, Konaga, Chiyanokomakumaki, Chiyamahamaki, Momomoshiniga, Pear Himeshingui, Mikanhamogorigami, Chinomonogoshiga, Chinomonogiga Kamiga, Kobu nomeiga, Yochi bitten bean corn poler, American white cockroach, Suzima larva, Heliotis genus, Helicoverpa genus, Agrotis genus, Iga, Kodolinga, ⁇ ⁇
  • Hemiptera pests for example, peach aphid, mosquito aphid, red radish aphid, wheat viper aphid, scorpion beetle, scorpion beetle, ssamoptera serrata, skull stag beetle, ssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssss.
  • Pear beetle flying beetle force, dark beetle force, shiro-louka, tsumaguro leafhopper, etc.
  • Coleoptera pests for example, Lepidoptera, Beetle, Colorado potato beetle, rice Dipter beetles, stag beetles, azuki beetles, mamekogane, himekogane, diablotica, tobacco beetle, platypus beetle, pine beetle longhorn beetle, sesame beak beetle, genus agliotis, swelling insects, etc.
  • House flies oak blow flies, Sentinic flies, Periform flies, Mycophores flies, Tane flies, rice hammogli flies, key flies, Drosophila melanogaster, sand flies, Koga squid moss force, Nesuna esima power, Shinahamadara power, etc.
  • Thrips pests for example, Thrips palmi Karny, Thrips palmi, etc., Hymenoptera, pests, for example, Diplomatidae, Rhododendron, Dermatophagoides, Orthoptera, pests, for example, Tonosamabatu, etc.
  • Reticulate pests for example, Japanese cockroaches, cockroaches, black cockroaches, etc.
  • Isoptera pests for example, house termites, japonicus, etc.
  • Lepidoptera for example, human flea, lice, for example, Lice, for example, human lice, ticks, for example, Namihadani, Kansahadahada2, Citrus spider mite, Apple spider mite, Mikansapidanii, Apple sabida2, Tyanohocolidina, Brevipalpas, Jeoptera nicas , Robin's mite, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Robin's mite, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Dermatophagoides farinae, Robin's mite, Dermatophagoides farinae, Dermatophagoides farin
  • Plant-parasitic nematodes for example, sweet potato nematode, negusarecentiyu, soybean cyst centiyu, rice singarecentiyu, matsunoza centiyu, etc.
  • Many insect pests such as aphids and aphids have developed resistance to organophosphorus agents, carbamates and acaricides, and have caused problems with the lack of efficacy of these agents. Effective drugs are needed.
  • the compound of the present invention is an agent having an excellent insecticidal and acaricidal effect against not only susceptible strains but also pests of an organophosphate, carbamate or pyrethroid-resistant strain and mites of acaricide-resistant strains.
  • the compound of the present invention is a highly safe drug with little phytotoxicity, low toxicity to fish and warm-blooded animals.
  • Example 1 Example 1
  • Example 1 By mixing and dissolving the above, an emulsion containing 10% of the active ingredient is obtained.
  • Example 15 Granule wettable powder
  • Test Example 1 Efficacy against tabular beetle
  • the seeds germinated 10 days after sowing in a three-dimensional bowl were inoculated with an adult of Aphid aphid ⁇ 1 day after the inoculation, the adults were removed, and the cucumber parasitized by the nymphs produced was shown in Example 11 of the drug.
  • the drug diluted with water was sprayed so that the compound concentration was 125 ppm. They were placed in a constant temperature room at a temperature of 25 ° C and a humidity of 65%, and after 5 days, they were examined for viability and the insecticidal rate was determined. The test was performed in duplicate.
  • Table 9 shows the results.
  • Test example 2 Efficacy against aphalt According to the formulation of the wettable powder described in Example 10 of the above-mentioned drug, it was diluted with water so that the compound concentration became 125 ppm. Corn leaves were immersed in the chemical solution for 30 seconds, air-dried, placed in a petri dish covered with filter paper, and inoculated with 5 larvae of 2nd instar larvae. They were covered with a glass lid and placed in a thermostatic chamber at a temperature of 25 and a humidity of 65%, and after 5 days, they were examined for viability and the insecticidal rate was determined. The test is in duplicate. Table 9 shows the results.
  • insecticidal rates of the following known compounds used as controls were all 0%.
  • Control compound (A) A compound described in JP-A-53-92769.
  • Control compound (B) The compound described in JP-A No. 555-154963.
  • Control compound (C) The compound described in EP18989.
  • Control Compound (D) The compound described in JP-A-55-154629.
  • Control compound (E) The compound described in JP-A-10-298169, WO95 / 29591. Test Example 3 Efficacy against Citrus red mites
  • Example 10 After 15 to 10 days after germination of the wings inoculated in a three-size bowl, 15 adult females of Nami-nada mosquito resistant to organophosphorus acid were inoculated, and the results are shown in Example 10 of the drug.
  • a chemical solution diluted with water was applied so that the compound concentration became 125 ppm. They were placed in a thermostatic chamber at a temperature of 25 ° C and a humidity of 65%, and after 3 days, they were examined for viability and the insecticidal rate was determined. The test is in duplicate.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne des composés acrylonitrile représentés par la formule générale (1) ; un procédé de préparation desdits composés; et des agents pesticides caractérisés en ce qu'ils renferment un ou plusieurs de ces composés comme ingrédient actif. Dans ladite formule, A désigne un groupe représenté par les formules générales A1, A2, A3, A4, A5 ou A6 : (où X1, X2, X3, X4, X5, X6 et X7 représentent chacun halogéno, C1-6alkyle ou analogue) ; B désigne un phényle pouvant être substitué par W2 ou un groupe hétérocyclique pouvant être substitué par W2; R représente C1-12alkyle, C1-6haloalkyle, C1-6alcoxy ou analogue; Y1 représente oxygène, soufre ou analogue; Y2 représente oxygène ou soufre; et Z1 et Z2 représentent chacun indépendamment hydrogène ou C1-6alkyle, à moins que Z1 et Z2 forment, avec l'atome de carbone auquel ils sont liés, un cycle à 5 ou 8 éléments.
PCT/JP2001/002096 2000-03-17 2001-03-16 Composes acrylonitrile et agents pesticides Ceased WO2001068589A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001241170A AU2001241170A1 (en) 2000-03-17 2001-03-16 Acrylonitrile compounds and pest controllers

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JP2000075813 2000-03-17
JP2000-75813 2000-03-17
JP2000152581 2000-05-24
JP2000-152581 2000-05-24
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007100160A1 (fr) * 2006-03-03 2007-09-07 Nissan Chemical Industries, Ltd. Composes acrylonitrile
US7649104B2 (en) 2003-03-28 2010-01-19 Nissan Chemical Industries, Ltd. Process for producing acrylonitrile compound
CN104650063A (zh) * 2013-11-25 2015-05-27 中国中化股份有限公司 一种2,4-二甲基恶唑基丙烯腈类化合物及其应用
CN108570008A (zh) * 2017-03-14 2018-09-25 浙江省化工研究院有限公司 一类吡唑类衍生物、其制备方法及应用
CN110003111A (zh) * 2018-01-04 2019-07-12 浙江省化工研究院有限公司 一种2-芳基-3-醚基-3-吡唑丙烯腈类化合物的制备方法
WO2019222912A1 (fr) * 2018-05-22 2019-11-28 浙江省化工研究院有限公司 Dérivés de pyrazole, leur procédé de préparation et leur utilisation
CN111771897A (zh) * 2019-04-04 2020-10-16 浙江省化工研究院有限公司 一种含唑醚螨腈和噻螨酮的杀螨组合物
CN111789122A (zh) * 2019-04-09 2020-10-20 浙江省化工研究院有限公司 一种含唑醚螨腈和螺环季酮酸类农药的杀螨组合物

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US4153705A (en) * 1977-01-26 1979-05-08 Schering Aktiengesellschaft Thiazolyl cinnamic acid nitriles, pesticides containing the same
US4297361A (en) * 1979-05-17 1981-10-27 Schering Aktiengesellschaft Thiazolylidene-oxo-propionitriles, insecticidal composition containing these compounds
EP0189960A2 (fr) * 1985-02-01 1986-08-06 Shell Internationale Researchmaatschappij B.V. Dérivés insecticides du 1,3-thiazole
EP0706758A1 (fr) * 1994-04-28 1996-04-17 IHARA CHEMICAL INDUSTRY Co., Ltd. Agent d'antifouling marin
JPH10298169A (ja) * 1997-04-22 1998-11-10 Ihara Chem Ind Co Ltd 漁網防汚剤

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Publication number Priority date Publication date Assignee Title
US4153705A (en) * 1977-01-26 1979-05-08 Schering Aktiengesellschaft Thiazolyl cinnamic acid nitriles, pesticides containing the same
US4297361A (en) * 1979-05-17 1981-10-27 Schering Aktiengesellschaft Thiazolylidene-oxo-propionitriles, insecticidal composition containing these compounds
EP0189960A2 (fr) * 1985-02-01 1986-08-06 Shell Internationale Researchmaatschappij B.V. Dérivés insecticides du 1,3-thiazole
EP0706758A1 (fr) * 1994-04-28 1996-04-17 IHARA CHEMICAL INDUSTRY Co., Ltd. Agent d'antifouling marin
JPH10298169A (ja) * 1997-04-22 1998-11-10 Ihara Chem Ind Co Ltd 漁網防汚剤

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7649104B2 (en) 2003-03-28 2010-01-19 Nissan Chemical Industries, Ltd. Process for producing acrylonitrile compound
US8138368B2 (en) 2003-03-28 2012-03-20 Nissan Chemical Industries, Ltd. Process for producing acrylonitrile compound
US8324420B2 (en) 2003-03-28 2012-12-04 Nissan Chemical Industries, Ltd. Process for producing acrylonitrile compound
WO2007100160A1 (fr) * 2006-03-03 2007-09-07 Nissan Chemical Industries, Ltd. Composes acrylonitrile
CN104650063A (zh) * 2013-11-25 2015-05-27 中国中化股份有限公司 一种2,4-二甲基恶唑基丙烯腈类化合物及其应用
CN104650063B (zh) * 2013-11-25 2017-11-28 沈阳中化农药化工研发有限公司 一种2,4‑二甲基恶唑基丙烯腈类化合物及其应用
CN108570008A (zh) * 2017-03-14 2018-09-25 浙江省化工研究院有限公司 一类吡唑类衍生物、其制备方法及应用
CN108570008B (zh) * 2017-03-14 2020-07-28 浙江省化工研究院有限公司 一类吡唑类衍生物、其制备方法及应用
CN110003111A (zh) * 2018-01-04 2019-07-12 浙江省化工研究院有限公司 一种2-芳基-3-醚基-3-吡唑丙烯腈类化合物的制备方法
CN110003111B (zh) * 2018-01-04 2020-11-13 浙江省化工研究院有限公司 一种2-芳基-3-醚基-3-吡唑丙烯腈类化合物的制备方法
WO2019222912A1 (fr) * 2018-05-22 2019-11-28 浙江省化工研究院有限公司 Dérivés de pyrazole, leur procédé de préparation et leur utilisation
AU2018424208B2 (en) * 2018-05-22 2020-04-30 Sinochem Lantian Co., Ltd Pyrazole derivative
US11104648B2 (en) * 2018-05-22 2021-08-31 Zhejiang Research Institute Of Chemical Industry Co., Ltd. Pyrazole derivative
CN111771897A (zh) * 2019-04-04 2020-10-16 浙江省化工研究院有限公司 一种含唑醚螨腈和噻螨酮的杀螨组合物
CN111789122A (zh) * 2019-04-09 2020-10-20 浙江省化工研究院有限公司 一种含唑醚螨腈和螺环季酮酸类农药的杀螨组合物

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