WO2005068443A1 - Acrylonitriles et agents pesticides - Google Patents

Acrylonitriles et agents pesticides Download PDF

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Publication number
WO2005068443A1
WO2005068443A1 PCT/JP2005/000569 JP2005000569W WO2005068443A1 WO 2005068443 A1 WO2005068443 A1 WO 2005068443A1 JP 2005000569 W JP2005000569 W JP 2005000569W WO 2005068443 A1 WO2005068443 A1 WO 2005068443A1
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Prior art keywords
group
alkyl
formula
alkoxy
alkylamino
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PCT/JP2005/000569
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English (en)
Japanese (ja)
Inventor
Jyun Iwata
Yukuo Mukohara
Makio Yano
Daisuke Hanai
Masao Yamaguchi
Hironori Furukawa
Keiji Koizumi
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Nippon Soda Co., Ltd.
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Priority to JP2005517106A priority Critical patent/JP4405971B2/ja
Publication of WO2005068443A1 publication Critical patent/WO2005068443A1/fr

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    • 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
    • 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

Definitions

  • the present invention relates to a novel acrylonitrile conjugate with reduced toxicity and a pesticidal agent.
  • An object of the present invention is to provide a novel compound which can be industrially advantageously synthesized, has a reliable effect, has reduced toxicity, and can be used as a pesticide which can be used safely.
  • the present invention has the formula (1)
  • A represents a group represented by the following formula [2].
  • E is an oxygen atom, a sulfur atom, a methylene group, a C alkyl group
  • R 11 R ′′ each independently represents a halogen atom or a C alkyl group
  • X is nitro, cyano, halogen, C alkyl, C haloalkyl, C
  • n is an integer of 2 or more, Xs may be the same or different.
  • X 1 is a hydrogen atom, a halogen atom, a C alkyl group, a C haloalkyl group, a C
  • 1-6 1-6 1-6 May be substituted with a carbonyl group, C cycloalkyl group or W 1 ! /, Phenyl group
  • U is a hydroxyl group, a nitro group, a cyano group, a halogen atom, an oxo group, a thioxo group, a C
  • U may be the same or different.
  • W 1 is a nitro group, a cyano group, a halogen atom, a C alkyl group, a C cycloalkyl group,
  • a plurality may be the same or different and substituted.
  • B is substituted with W 2, I even / Hue - !!! substituted with group or W 2, also O /, represents a heterocyclic group.
  • w 2 represents a cyano group, a nitro group, a halogen atom, a C alkyl group, a C
  • w 2 are the same Yogumata W 2 be a plurality of substituents or different and is 4 one 8-membered ring together with the adjacent bonded atoms atoms May be formed.
  • heterocyclic group in heterocyclic group which may be substituted with w 2 is Toriazoriru, thiazolyl, O Kisazoriru, Isookisazoriru, isothiazolyl, pyrazolyl, imidazolyl, tetrazolyl, Okisajiazoriru, thiadiazolyl, thienyl, furyl, pyrrolyl, pyridyl, Piridaji -Le, pyrimidyl, and pyrajurka are also a group.
  • G is a hydrogen atom, a C alkyl group, a phenyl C alkyl group which may have a substituent,
  • R 1 is a C alkyl group, C cycloalkyl group, C haloalkyl group, C
  • 1-6 represents an alkoxy group or a substituted or unsubstituted phenyl group
  • R 2 may have a C alkyl group or a substituent, and represents a fuel group
  • R 3 is a C alkyl group, C haloalkyl group, C alkoxy group, C alkoxy
  • Y 1 may be substituted with an oxygen atom, a sulfur atom or a C alkyl group to form a nitrogen atom.
  • Y 2 may be substituted with an oxygen atom, a sulfur atom or a C alkyl group
  • z 1 and z 2 are each independently substituted with a hydrogen atom, a c alkyl group or w 1
  • p and q each independently represent 0 or an integer of 1 to 3. However, the number of atoms forming a ring is 4 or more.
  • E is an oxygen atom, sulfur atom, methylene group , Methyl, ethyl, n-propyl, isopropyl, etc.
  • the lengths 11 and R 12 are each independently a halogen atom such as fluorine, chlorine, bromine, and iodine; methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and t.
  • C alkyl group such as butyl halogen atom or C alkyl
  • 1-6 represents 1-6 groups.
  • X is a nitro group; a cyano group; a halogen atom such as fluorine, chlorine, bromine and iodine; methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t C alkyl groups such as butyl; chloromethyl, fluoromethyl, bromomethyldi Such as chloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluorophenol, pentachlorophenol, etc.
  • sec C alkoxy groups such as butoxy, isobutoxy, t-butoxy; chloromethoxy, dichloro
  • C haloalkoxy groups such as romethoxy, trichloromethoxy, trifluoromethoxy, 1-fluoroethoxy, 1,1-difluoroethoxy; methylthio, ethylthio, n-propylthio,
  • C alkylthio groups such as isopropylthio, n-butylthio, isobutylthio, sec-butylthio, t-butylthio, etc .; methylsulfiel, ethylsulfyl, propylsulfur
  • C-anolequinolenesolefino-nore group such as cinnolenole, butinolesnorefinee
  • C anorequinorenoreho such as chinoresnorehonore, propinoresnoreho-nore, butinoresnoreho-nore
  • C-amino group such as methylamino, ethylamino, isopropylami with n-propylami n, isobutylami with n-butylami, sec-butylami, t-butylami, 1 methylbutylami, n pentylamino, etc .;
  • Di-c-alkylamino groups such as lumino, dibutylamino, ethylpropylamino, methylpropylamino, etc .; methyl carbyl, ethyl carbyl, propyl
  • C alkylcarbyl groups such as rubonyl and butylcarbon; or methoxycarb
  • C alkoxycarbonyl groups such as boninole, ethoxycanoleboninole, n-propoxycanoleboninole, isopropoxycanoleboninole, n-butoxycarbol, and t-butoxycarbol
  • n 0 or an integer of 1 to 3.
  • Xs may be the same or different.
  • X 1 is a hydrogen atom; a halogen atom such as fluorine, chlorine, bromine and iodine; and a carbon atom such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl.
  • 1-6 alkyl group chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl, pentafluoroethyl, etc.
  • c haloalkyl group methoxy
  • C-alkoxycarbon groups such as canoleboninole, ethoxycanoleboninole, n-propoxycanoleboninole, isopropoxycanolebonil, n-butoxycarbol, and t-butoxycarbol
  • a C cycloalkyl group such as cyclopropyl, cyclopentyl, cyclohexyl and the like; or
  • W 1 ! which represents a phenyl group.
  • U is a hydroxyl group; a nitro group; a cyano group; a halogen atom such as fluorine, chlorine, bromine, or iodine; an oxo group; a oxo group; methyl, ethyl, n-propyl, isopropyl, n-butyl, and sec-butyl.
  • C alkyl groups such as, isobutyl and t-butyl; cyclopropyl, cyclobutyl
  • Cycloalkyl groups such as, cyclopentyl and cyclohexyl; chloromethyl, fluoro
  • C-haloalkyl groups such as methyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl, and pentafluoroethyl; methoxy, ethoxy, n Propoxy, iso
  • C-alkoxy such as propoxy, n -butoxy, sec butoxy, isobutoxy, t-butoxy
  • c-haloalkoxy groups such as chloromethoxy, dichloromethoxy, trichloromethoxy, trifluoromethoxy, 1-fluoro-mouth ethoxy, 1,1-difluoroethoxy; methylthio, ethyl
  • C alkylthio groups such as thio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, t-butylthio, etc .; methylsulfiel, ethylsulfur
  • C-Anolequinorenorefi-nore such as fine-nore, propinoresnoreno-nore, butinoresnoreno-nore
  • Di-C alkylamino groups such as methylpropylamino, methylbutylamino, etc .; methylcarbyl, ethyl
  • C alkylcarbonyl such as carbonyl, propylcarbonyl, butylcarbonyl, etc.
  • 1-6 represents a coxicarbyl group.
  • the substitution position can be selected at any position on the ring, and when substituted plurally, they may be substituted with the same or different substituents. Two identical carbon atoms on the ring may be simultaneously substituted.
  • w 1 is a nitro group; a cyano group; a halogen atom such as fluorine, chlorine, bromine and iodine; an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl; Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
  • C cycloalkyl groups such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl
  • C alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy, or chloromethoxy, dichloromethoxy
  • w 1 is the same or different and
  • B is substituted with W 2, I even / Hue - !!! substituted with group or W 2, also O /, represents a heterocyclic group.
  • W 2 represents a cyano group; a nitro group; a halogen atom such as fluorine, chlorine, bromine, and iodine; methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, etc.
  • DC Alkyl group ether, 1-probe, 2-probe, 1-butule, 2-bute
  • C haloalkyl groups such as methinole, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl, and pentafluoroethyl; methoxy, ethoxy, n-propoxy,
  • C-alkoxy such as propoxy, n -butoxy, sec butoxy, isobutoxy, t-butoxy
  • 1-6 groups chloromethoxy, dichloromethoxy, trichloromethoxy, trifluoromethoxy, 1-fluoro C-haloalkoxy groups such as mouth ethoxy and 1,1-difluoroethoxy; cyclopropyl, cyclopropyl
  • C cycloalkyl groups such as robutyl, cyclopentyl and cyclohexyl; methylthio,
  • C alkylthio groups such as ethylthio, npropylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, t-butylthio, etc .;
  • C anore quinoresore such as chinoresorerefore, propinoresorerefore, butinoresorerefore
  • Fininole group C alkylsulfol group such as methinoles-no-le-honinole, etinoles-no-le-hon-inole, propinoles-no-le-hon-inole, butinores-noreno-hole; methylaminoethylamino, n-propylamino
  • C-alkylamino groups such as isopropylami, n-butylami-containing isobutylami-sec, sec-butylami-containing t-butylamino, etc .;
  • C alkylcarbon group such as butylcarbon; methoxycarbon, ethoxycar
  • C alkoxycarbonyl such as bonyl, propoxycanoleboninole, butoxycarbonyl
  • w 2 may be the same or different and may be substituted plurally. Further, w 2 may form a 418-membered ring together with the atom adjacent to the bonding atom.
  • W 2 Yo heterocyclic group of the heterocyclic group, Toriazoriru, thiazolyl, O Kisazoriru, Isookisazoriru, isothiazolyl, pyrazolyl, imidazolyl, tetrazolyl, Okisajiazoriru, thiadiazolyl, thienyl, furyl, pyrrolyl, pyridyl, Pyridazyl, pyrimidyl, pyrajurka are also a group of forces.
  • G is a hydrogen atom; C alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and its isomers; Benzyl, 1-Fu-ruethyl, 2-Fu-ruethyl, 1 Hue-
  • R 1-Methylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, etc. may have a substituent, phenyl C alkyl group; methoxymethyl, methoxyethyl
  • Alcohols such as, ethoxyxetil, ethoxymethyl, propoxymethyl, butoxymethyl
  • R 1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl and its isomer, n-hexyl and its isomer, C-alkyl groups such as n-heptyl and its isomers, n-nor and its isomers, n-dodecyl and its isomers; cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl
  • C cycloalkyl groups such as xyl; chloromethyl, fluoromethyl, bromomethyl, dicyl
  • C such as oral methyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl, pentafluoroethyl, etc.
  • 1-6 haloalkyl group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy; methylthio, ethylthio
  • C alkylthio groups such as n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, t-butylthio, etc .; methylamidoethylamino, n-propyl
  • C alkylamino groups such as lumino, isopropylami n n butylami in isobutylami in sec butylami in t butylami in 1 methylbutylami n n pentylamino
  • a di-C alkylamino group such as dimethylamino, getylamino, dipropylamino, dibutylamino, methylpropylamino with methylpropylamino, etc .;
  • Examples of the group include benzyloxy, 1-phenylethoxy, 2-phenylethoxy, 1phenyl 1methylethoxy, 1phenylpropoxy, 2phenylpropoxy, 3phenylpropoxy and the like.
  • R 2 is methyl, Echiru, n-propyl, isopropyl, n- butyl, isobutyl, sec- butyl Le, t - butyl, n - pentyl and its isomers, n - hexyl and its isomers, n - heptane Cyl and its isomers, n-nor and its isomers, n-dodecyl and its isomers (C alkyl group; or a substituted or unsubstituted phenyl group).
  • R 3 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl and its isomer, n-hexyl and its isomer, n- C alkyl groups such as heptyl and its isomers, n-nonyl and its isomers, n-dodecyl and its isomers; chloromethyl, fluoromethyl, bromomethyl, dichloromethyl,
  • alkoxy groups such as butoxy, isobutoxy, and t-butoxy; methoxymethyl,
  • C alkoxy C alkyl group such as toxityl, ethoxymethyl, ethoxymethyl, propoxymethyl, butyroxymethyl; methylthio, ethylthio, npropylthio, iso
  • Alkylthio groups such as propylthio, n-butylthio, isobutylthio, sec-butylthio, t-butylthio, etc .; methylthiomethyl, methylthioethyl, ethylthioethyl,
  • alkylthio C such as ethylthiomethyl, propylthiomethyl and butylthiomethyl
  • Di-C-alkylamino groups such as dipropylamino-containing dibutylamino, ethylpropylamino, methylpropylamido-methylbutylamino, etc .;
  • 1-6 3-6 kill group may have a substituent, phenyl C alkyl group; may have a substituent!
  • a phenylthio C alkyl group or a substituted or unsubstituted phenyl group.
  • substituent of the phenyl group which may have a R 2 and R 3 definitive substituents, fluorine, chlorine, bromine, halogen atom such as iodine; methyl, Echiru, n-propyl, isopropoxy port pill C alkyl group such as n-butyl, sec-butyl, isobutyl, t-butyl, etc.
  • C-haloalkyl groups such as methyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl, and pentafluoroethyl; methoxy, ethoxy, n-
  • alkoxy groups such as propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, and t-butoxy.
  • Y 1 represents an oxygen atom, a sulfur atom, a hydrogen atom, or a nitrogen atom substituted by a C alkyl group such as methyl, ethyl, propyl, etc.
  • Y 2 represents an oxygen atom, a sulfur atom or a hydrogen atom, or a nitrogen atom substituted by a C alkyl group such as methyl, ethyl and propyl;
  • z 1 and z 2 are each independently a hydrogen atom, methyl, ethyl, propyl, etc.
  • Hue - force represents a group or, z 1 and z 2 Togayui combined and connexion cyclopropyl such together with the carbon atom, cyclobutyl, cyclopentyl, A 3- to 8-membered ring such as cyclohexyl, cycloheptyl, cyclooctyl and the like may be formed.
  • It is a compound represented by.
  • B represents the following formula B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, B Compounds selected from —9 and B—10 are preferred.
  • X is a hydrogen atom; a cyano group; a nitro group; a C alkyl group such as methyl, ethyl, ⁇ -propyl, isopropyl, ⁇ -butyl, sec-butyl, isobutyl, and t-butyl; chloromethyl
  • Haloalkyl groups such as chloro, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, trichloroethyl, trifluoroethyl and pentafluoroethyl; methoxy, ethoxy, n
  • C _ alkoxy group such as oxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy; chloromethoxy, dichloromethoxy, trichloromethoxy, trifluoromethoxy
  • C haloalkoxy groups such as, 1 fluoroethoxy and 1, 1 difluoroethoxy
  • C alkylthio groups such as n-, ethynolethio, n -propylthio, isopropylthio, n-butynolethio, isobutynolethio, sec-butylthio, t-butylthio; methylsulfiel,
  • C-Anolequinores such as etinoresnorefi-nore, propinoresnorefi-nore, butinoresnorefi-nore
  • Norefininole group C alkylsulfol group such as methinolesnorlehoninole, ethinolesnorlehoninole, propinoresnorlehoninole, and butynolesulfol; methylethylethylamine, n-propylamino C-alkylamino groups such as isopropylamido-containing n-butylamido-containing isobutylamido-containing sec butylamido-containing t-butylamino, 1-methylbutylamido-n-pentylamino, etc .;
  • Di-C-alkylamino groups such as methylpropylamino and methylbutylamino;
  • C alkyl such as bonyl, ethylcarbonyl, propylcarbonyl, butylcarbonyl, etc.
  • C alkoxycarbonyl group such as methoxycarbon, ethoxycarbon, n-propoxycarbon, isopropoxycarbonyl, n-butoxycarbonyl, t-butoxycarbonyl; may have a substituent , A phenyl group; or having a substituent
  • it represents a phenoxy group.
  • X 2 and X 3 each independently represent a substituent represented by X 4 or a halogen atom such as fluorine, chlorine, bromine and iodine.
  • One of the features of the compound of the present invention is that its toxicity is reduced as compared with the compound of the prior art which has only insecticidal activity. Toxicity was determined by combining methods known in the literature, such as the “Pharmacokinetic Testing Guidelines” (Ministry of Health, Labor and Welfare), “Drug Metabolism Experiments” (edited by the Japan Isotope Association, Maruzen), and “Drug Metabolism” (Tokyo Kagaku Dojin). Acute and long-term toxicity can be predicted for teeth (rats, mice, etc.), egrets, dogs, etc. In addition, the prediction of long-term toxicity for the above animals can also be determined by evaluating protein binding properties, blood kinetics, S9mix metabolism, and the like.
  • the compound of the present invention can be produced, for example, by the following method.
  • L represents a halogen atom, a C alkoxy group
  • a compound represented by the formula [7] can be obtained by reacting a compound represented by the formula [5] with a compound represented by the formula [6] in the presence of a base.
  • Examples of the base used in this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, sodium methoxide, potassium hydroxide, and magnesium.
  • Metal alkoxides such as ethoxide, organic metals such as n-butyllithium and lithium diisopropylamide (LDA), metal hydrides such as sodium hydride and potassium hydride, and organic bases such as triethylamine, diisopropylamine and pyridine.
  • Solvents that can be used include N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), acetonitrile, hexamethylphosphoramide (HMPA), benzene, toluene, dichloromethane, and chloroform , Tetrachloride carbon or an organic base can be used as a solvent.
  • the reaction temperature can be arbitrarily selected from the temperature range from 78 ° C. to the boiling point of the solvent to be used, depending on conditions such as the base and the leaving group.
  • phase transfer catalyst such as a quaternary amine salt and a base such as sodium hydroxide or potassium hydroxide are mixed in a two-phase solvent of benzene, toluene, dichloromethane, chloroform, carbon tetrachloride or the like and water.
  • the reaction is carried out in a temperature range up to the boiling point of the solvent used at -78 ° C. to obtain the conjugated compound represented by the formula [7].
  • the compound represented by the formula [7] exists as a keto-type or enol-type tautomer as shown in the following figure.
  • the structure is mainly determined as an enol type in keto-type and enol-type tautomerism, but these two isomers are all included in the scope of the present invention.
  • G ′ represents a group excluding a hydrogen atom in the definition of G
  • L represents a halogen atom, p-toluenesulfo-oxy group , Methanesulfo
  • Examples of the base used in this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, sodium methoxide, potassium hydroxide and magnesium.
  • Examples include metal alkoxides such as ethoxide, organic metals such as n-butyllithium and LDA, metal hydrides such as sodium hydride and potassium hydride, and organic bases such as triethylamine, diisopropylamine, pyridine and the like.
  • reaction temperature is preferably in the temperature range from ⁇ 78 ° C. to the boiling point of the solvent used.
  • a phase transfer catalyst such as a quaternary amine salt and a base such as sodium hydroxide and potassium hydroxide are mixed in a two-phase solvent of benzene, toluene, dichloromethane, chloroform, carbon tetrachloride, etc. and water.
  • the compound represented by the formula [1] or [1 ′] can be obtained by carrying out a reaction in a temperature range up to the boiling point of a solvent using -78 ° C.
  • the compound of the present invention represented by the general formula [1] has a stereoisomer as shown below, and depending on the reaction conditions and the purification method, any one of the two isomers may be used. In some cases, only one isomer may be obtained, or as a mixture of two isomers. All of these isomers are included in the scope of the present invention.
  • compounds having an asymmetric carbon and having an optical isomer may be present.
  • optically active substance is also included in the present invention.
  • 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, MS and the like.
  • Table 1 shows typical examples of the compounds of the present invention that can be produced as described above.
  • the abbreviations in the table have the following meanings.
  • the compound of the present invention is useful as an active ingredient of a pesticidal agent, and is particularly useful as an insecticide, acaricide, nematocide, a sanitary insecticide, and an antifouling agent in water.
  • a pesticidal agent for example, a wettable powder, a granule, It can also be used in the form of powders, emulsions, aqueous solvents, suspensions, wettable powders and the like.
  • a solid agent When a solid agent is intended as an additive and a carrier, mineral powder such as soybean grains, vegetable powder such as flour, diatomaceous earth, apatite, gypsum, talc, bentonite, neurophilite, clay, etc. Organic and inorganic compounds such as sodium benzoate, urea and sodium sulfate are used.
  • kerosene, xylene and petroleum-based aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, methyl isobutyl ketone, mineral oil, vegetable oil , Water, etc. can be used as the solvent.
  • a surfactant may be added, if necessary.
  • the surfactant for example, alkyl ethers added with polyoxyethylene, higher fatty acid esters added with polyoxyethylene, higher sorbitan fatty acid esters added with polyoxyethylene, and polyols
  • Nonionic surfactants such as tristyryl phenyl ether to which xylene is added, sulfates of alkyl phenol ethers to which polyoxyethylene is added, alkyl naphthalene sulfonates, polycarboxylates, and ligand sulfonic acids. Salts, formaldehyde condensates of alkyl naphthalene sulfonates, isobutylene-maleic anhydride copolymers, and the like.
  • the amount of the active ingredient in the preparation is preferably 0.01 to 90% by weight, particularly preferably 0.05 to 85% by weight.
  • the wettable powders, emulsions, suspensions, aqueous solvents, granule hydrates, etc. obtained in this way are diluted to a predetermined concentration with water to obtain solutions, suspensions or emulsions, which are powder-granules. Is applied directly to plants or soil.
  • 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, pesticides or synergists. Wear.
  • fungicides insecticides, acaricides, and plant growth regulators that can be used by mixing with the compound of the present invention are shown below.
  • Capbutane Forpet, Thiuram, Ziram, Zineb, Maneb, Mancozeb, Propineb, Polycarbamate, Chlorotatin, Quintosen, Captafor, Iprodione, Prosimidon, Vinclozolin, Fluorimide, Thymoxal, Meprol, Flutral , Pencyclon, oxycarboxine, fosetylaluminum, propamocarb, triadimefon, triadimenol, propiconazole, diclobutrazole, bitertanol, hexaconazone, microbutaninole, funorecilazole, etaconazo monole, funo Leotrimazol, Flutriafen, Penconazole, Diniconazole, Cyproconazoles, Fuenarimol, Triflumizole, Prochloraz, Imazalil, Difrazoate, Tridede Noref, phenpropimonoref,
  • Triphenyltin hydroxide diethofencalp, metasulfocarb, quinomethionate, binapataryl, lecithin, baking soda, dithianon, dinocap, phenaminosulf, diclomedine, guazatine, dozine, IBP, edifenphos, mepa-pyrim, phenolemzone, triclamide, Metasulfocarp, fluazinam, etoquinolak, dimethomorph, pyroquilon, techopent phthalam, fusalide, phenazine oxide, thiabendazole, tricyclazole, vinclozolin, simoxal, cyclobutayl, guazatine, propamocalp hydrochloride, oxolinic acid.
  • Pest control agents [0091] Pest control agents
  • Difnolebenzuron Chlorfluazuron, Hexaflumuron, Trifnolemuron, Tetrabenduron, Funorefenoxuron, Funolecyclotasulone, Buprofezin, Pyriproxyfen, Metoprene, Benzoepin, Diafentiuron, Imidacloprid,- Tembiram, acetamiprid, cartap, thiocyclam, bensultap, chlorfenavir, emamethatin benzoate, tebufenozide, fiprole, nicotine sulfate, rotenone, methaldehyde, machine oil, microbial pesticides such as BT and insect pathogenic virus.
  • Plant growth regulator Gibberellins (eg, gibberellin A3, gibberellin A4, gibberellin A7), IAA, NAA 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, nymphicidal, larvicidal, and ovicidal action.
  • the following are typical examples.
  • Lepidopteran insect pests for example, Spodoptera litura, Spodoptera, Tamanayaga, Aomushi, Tamanagin ⁇ ⁇ ⁇ , Konaga, Chiyanokokakumon Hamaki, Chiyamahamaki, Momosintaiga, Nashihimeshingui, Citrus serrata, Chinohogasogama, Chinohosogamaiga, Chinohosogamaigami [0097] Hemiptera pests, such as peach aphid, peter aphid, etc. -Betula aphid
  • Wheat beetle aphid Lycopodium elegans, Aedes beetle, Anemone aphid, Anopheles serrata, Aphid lice, Tobacco white lice, Psyllid lice, Psyllid lice, Tobira porphyra, Himetobi porphyra, etc.
  • Coleoptera pests for example, Lepidoptera, beetles, leaf beetles, colorado leaf beetles, rice beetle, scorpion beetle, azuki beetle, beetle beetle, beetle beetle, diablotica, tobacco beetle, giant leaf beetle, pine beetle, pine beetle , Kokunusuto, kamizomushi etc.,
  • Diptera insect pests for example, house flies, oak fly, centi-kuba, periminoe, mandarin fruit fly, flies, rice flies, tree mouth fly flies, sand flies, kota takaeka, aedesima power, shinamamadara power, etc.
  • Hymenoptera pests for example, Thrips palmi, Thrips palmi, etc.
  • Hymenoptera pests, for example, Diplomatidae, Rhododendron wasp, etc.
  • Orthoptera pests such as Tosamabata, Chiapana cockroaches, Scarlet cockroaches , Black crocodile, etc.
  • Isoptera pests for example, house termites, japonicus termites,
  • Lepidopteran pests for example, human fleas, lice pests, for example, human lice,
  • Mites for example, Nami-Nada, Nisenami-Nami, Kanza-Nami-Nada, Tangerine spider mite, Apple Hadani, Citrus sabida, Apple sabida, Chinohokorida, Brevipalpas, Gote tranicas, Robin mite, Scarab mite, Dermatophagoides farinae, Dermatophagoides farinae, Scarabidae
  • Plant-parasitic nematodes for example, sweet potato nematode, negusarecentiyu, dyscyst centipede, rice singarecentiyu, matsunozaentienyu, and the like.
  • Pests that are preferably applied are lepidopteran pests, Hemiptera pests, Coleoptera pests, Pteropoda pests, and Crustaceans, and particularly preferably Lepidoptera pests, Hemiptera pests, and Crustaceans.
  • many insect pests and mites such as moth moth, pinnacles, leafhoppers, aphids, and radish, have developed resistance to organophosphates, carbamates, and acaricides, and have caused a problem of insufficient efficacy of these agents.
  • the compound of the present invention is an agent having an excellent insecticidal and acaricidal effect against insects that are resistant not only to susceptible strains but also to strains resistant to organophosphates, carbamates and pyrethroids, and to mites that are resistant to acaricides.
  • the compound of the present invention is a highly safe drug with low toxicity to fish and warm-blooded animals with little phytotoxicity.
  • the compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to underwater contacts such as ship bottoms and fish nets.
  • reaction solution was returned to room temperature, 20 ml of an aqueous sodium acetate solution (3M) and 16 ml of hydrogen peroxide solution were sequentially added, and the mixture was stirred for 2 hours.
  • the reaction solution was poured into ice water, extracted with ethyl acetate, washed with saturated saline, and then the organic layer was concentrated under reduced pressure.
  • Table 2 shows the structural formula and physical constants of the compound of the present invention produced as described above.
  • composition of the present invention will be described.
  • the additives and the addition ratios can be changed over a wide range, which is not limited to these examples.
  • Parts in Examples of the preparations are parts by weight.
  • Lignesulfonic acid sodium salt 8 parts The above was uniformly mixed and finely pulverized to obtain a wettable powder with an active ingredient of 40%.
  • the above mixture is uniformly mixed and finely ground, then an appropriate amount of water is added and the mixture is kneaded to form a clay.
  • the clay is granulated and dried to obtain a wettable powder with an active ingredient of 40%.
  • composition of the present invention obtained as described above is applied as a pesticide are shown below.
  • Test example 1 Efficacy against petibug
  • Germination seeds sown 10 days after inoculation in three-sized pots were inoculated with adult Aphid aphids. One day later, the adult was removed, and a medicinal solution diluted with water was sprayed on the cucumber parasitized by the born nymphs according to the emulsion formulation shown in Formulation Example 2 so that the compound concentration became 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 is in duplicate. As a result, the following compounds showed 100% insecticidal rates. The compound numbers correspond to those in Table 2.
  • the insecticidal rate of pirimicarb used as a control was 9%.
  • Test example 2 Efficacy against aphalt
  • the compound was diluted with water so as to have a compound concentration of 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 five second instar larvae. With a glass lid, it was placed in a constant temperature room at a temperature of 25 ° C and a humidity of 65%, and after 5 days, the life and death were examined, and the insecticidal rate was determined. The test is in duplicate. As a result, the following compounds showed 100% insecticidal rates.
  • the compound numbers correspond to Table 2.
  • the control rate of chlordimeform was 40%.
  • the present invention provides a novel pesticidal agent having low toxicity and low residence.

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

Abstract

L'invention concerne des composés représentés par la formule générale [1] et des agents pesticides contenant ces composés en tant que principe actif : [1]. A représente thiazolyle substitué par un noyau condensé éventuellement substitué, B représente un groupe phényle éventuellement substitué ou un groupe hétérocyclique, et G représente un groupe représenté par la formule générale COR1 ou analogue.
PCT/JP2005/000569 2004-01-19 2005-01-19 Acrylonitriles et agents pesticides WO2005068443A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111803499A (zh) * 2018-06-13 2020-10-23 四川轻化工大学 一种治疗抗痛风、抗高尿酸血症的药物组合物ⅱ

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997040009A1 (fr) * 1996-04-25 1997-10-30 Nissan Chemical Industries, Ltd. Derives ethyleniques et agents pesticides
JPH11124306A (ja) * 1997-10-22 1999-05-11 Nissan Chem Ind Ltd 殺虫・殺ダニ・殺菌剤組成物
WO2003064401A1 (fr) * 2002-01-29 2003-08-07 Nippon Soda Co., Ltd. Composes acrylonitriles et pesticides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997040009A1 (fr) * 1996-04-25 1997-10-30 Nissan Chemical Industries, Ltd. Derives ethyleniques et agents pesticides
JPH11124306A (ja) * 1997-10-22 1999-05-11 Nissan Chem Ind Ltd 殺虫・殺ダニ・殺菌剤組成物
WO2003064401A1 (fr) * 2002-01-29 2003-08-07 Nippon Soda Co., Ltd. Composes acrylonitriles et pesticides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111803499A (zh) * 2018-06-13 2020-10-23 四川轻化工大学 一种治疗抗痛风、抗高尿酸血症的药物组合物ⅱ
CN111803499B (zh) * 2018-06-13 2021-09-14 四川轻化工大学 一种治疗抗痛风、抗高尿酸血症的药物组合物ⅱ

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