WO2013027864A1 - Composé ester et son utilisation - Google Patents

Composé ester et son utilisation Download PDF

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Publication number
WO2013027864A1
WO2013027864A1 PCT/JP2012/071937 JP2012071937W WO2013027864A1 WO 2013027864 A1 WO2013027864 A1 WO 2013027864A1 JP 2012071937 W JP2012071937 W JP 2012071937W WO 2013027864 A1 WO2013027864 A1 WO 2013027864A1
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Prior art keywords
configuration
formula
present
cyclopropane ring
substituent
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PCT/JP2012/071937
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English (en)
Inventor
Noritada Matsuo
Toru Uekawa
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Sumitomo Chemical Company, Limited
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Priority to CN201280041133.2A priority Critical patent/CN103781769B/zh
Publication of WO2013027864A1 publication Critical patent/WO2013027864A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
    • C07D233/78—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
    • C07D249/12—Oxygen or sulfur atoms

Definitions

  • the present invention relates to an ester compound and use thereof.
  • An object of the present invention is to provide a novel compound having an excellent pest control effect.
  • R 3 represents a C1-C4 alkyl group
  • a relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a trans configuration
  • a pest control agent comprising the ester compound according to any one of [1] to [10] or [1-2] and an inert carrier;
  • a method of controlling pests which comprises the step of applying an effective amount of the ester compound according to any one of [1] to [10] or [1-2] to pests or a place where pests inhabit;
  • a method of controlling pests which comprises the step of applying an effective amount of the ester compound according to any one of [1] to [10] or [1-2] to cockroaches or a place where cockroaches inhabit;
  • a method of controlling pests which comprises a step of spraying an effective amount of the ester compound according to any one of [1] to [10] or [1-2] to cockroaches or a place where cockroaches inhabit;
  • the compound of the present invention has an excellent pest control effect and is therefore useful as active ingredient for a pest control agent.
  • Examples of the C1-C4 alkyl group to be used herein include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group and tert-butyl group.
  • Each isomer having pest control activity or a mixture of those isomers in an arbitrary ratio is included in the present invention.
  • Examples of the compound of the present invention include the following compounds.
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) , that is, a compound represented by formula (a):
  • R 3 represents the same meanings as defined above, and a relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a trans configuration;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * , that is, a compound represented by formula (b) :
  • R 3 represents the same meanings as defined above, and a relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a trans configuration;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) ;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) , and a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration or a mixture of E configuration and Z configuration, and the proportion of the E configuration is 50% or more;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) , and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and the double bond of the substituent at the 3-position of the cyclopropane ring is in E configuration or a mixture of E configuration and Z configuration, and the proportion of the E configuration is 50% or more;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration, and a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration or a mixture of E configuration and Z configuration, and the proportion of the E configuration is 50% or more;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration or a mixture of E configuration and Z configuration, and the proportion of the E configuration is 50% or more;
  • a compound of represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration, and a double bond .present on the substituent at the 3-position of the cyclopropane ring is in E configuration;
  • a compound represented by formula (1) wherein a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration and R 3 represents methyl group;
  • a compound represented by formula (1) wherein an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is. 50% or more, and R 3 represents methyl group;
  • a compound represented by formula (1) wherein an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and R 3 represents tert-butyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and R 3 represents methyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration, and R 3 represents methyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents methyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration, and R 3 represents methyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) , and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration, and a double bond present on the substituent at the 3-position of the cylopropane ring is in E configuration . or a mixture of E configuration and Z configuration, and the proportion of the E configuration is 50% or more, and R 3 represents methyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an absolute configuration at the 1-position of the cyclopropane ring is an .
  • R configuration and a double bond present on the substituent at the 3-position of the cycopropane ring is in
  • R 3 represents methyl group
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration, and R 3 represents ethyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents ethyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration and R 3 represents ethyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cylopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents ethyl group;
  • a compound . represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cycopropane ring is in E configuration, and R 3 represents ethyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and R 3 represents isopropyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration, and R 3 represents isopropyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents isopropyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration, and R 3 represents isopropyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cylopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents isopropyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cycopropane ring is in E configuration, and R 3 represents isopropyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and R 3 represents tert- butyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration, and R 3 represents tert-butyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents tert-butyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration, and R 3 represents tert-butyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cylopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents tert-butyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -CH 2 -C * ( 0) and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cycopropane ring is in E configuration, and R 3 represents tert-butyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and R 3 represents methyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration, and R 3 represents methyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents methyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration, and R 3 represents methyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cylopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents methyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cycopropane ring is in E configuration, and R 3 represents methyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and R 3 represents ethyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration, and R 3 represents ethyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents ethyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration, and R 3 represents ethyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cylopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents ethyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cycopropane ring is in E configuration, and R 3 represents " ethyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents isopropyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration, and R 3 represents isopropyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an absolute configuration at.
  • the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cylopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents isopropyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (C . H 3 ) N * and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cycopropane ring is in E configuration, and R 3 represents isopropyl group.
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) * and R 3 represents ter-butyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents tert-butyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and a double bond present on the substituent at the 3-position of the cyclopropane ring is in E configuration, and R 3 represents tert-butyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH 3 ) N * and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cylopropane ring is in E configuration or a mixture of E configuration and Z configuration and the proportion of the E configuration is 50% or more, and R 3 represents tert-butyl group;
  • a compound represented by formula (1), wherein Q represents N (CH 2 C ⁇ CH) -C (CH3) N * and an absolute configuration at the 1-position of the cyclopropane ring is an R configuration and a double bond present on the substituent at the 3-position of the cycopropane ring is in E configuration, and R 3 represents tert-butyl group.
  • the compound of the present invention can be produced, for example, by the following processes.
  • R 3 represents the same meanings as described above, and the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a trans configuration
  • Examples of the reactive derivative include an acid halide of the carboxylic acid compound represented by formula (4), an acid anhydride of the carboxylic acid represented by formula (4), an ester of the carboxylic acid represented by formula (4) and the others.
  • Examples of the acid halide include an. acid chloride compound and an acid bromide compound, and examples of the ester include a methyl ester, an ethyl ester and the others.
  • the reaction is usually conducted in a solvent in the presence of a condensing agent or a base.
  • Examples of the condensing agent that are used in the reaction include dicyclohexylcarbodiimide and l-ethyl-3- ( 3- dimethylaminopropyl) carbodiimide hydrochloride.
  • Examples of the base that are used in the reaction include organic bases such as triethylamine, pyridine, N,N- diethylaniline, 4-dimethylaminopyridine and diisopropylethylamine .
  • solvents examples include hydrocarbons such as benzene, toluene and hexane; ethers such as diethylether and tetrahydrofuran; halogenated hydrocarbons such as chloroform, dichloromethane, 1 , 2-dichloroethane and chlorobenzene; and a mixture of these solvents; and the others.
  • the reaction time of the reaction is usually within a range from 5 minutes to 72 hours.
  • the reaction temperature of the reaction is usually within the range from -20°C to 100°C (from -20°C to a boiling point of a solvent in the . case that the boiling point of a solvent to be used is lower than 100°C) , and preferably from -5°C to 100°C (from -5°C to a boiling point of a solvent in the case that the boiling point of the solvent to be used is lower than 100°C) .
  • a molar ratio of the alcohol compound represented by formula (3) to the carboxylic acid compound represented by formula (4) or a reactive derivative thereof to be used can be arbitrarily set, and is preferably an equimolar ratio or a ratio close thereto.
  • the condensing agent or the base can be usually used in an arbitrarily proportion within the range from 0.25 mol to an excessive amount, and preferably from 0.5 mol to 2 mol, based on 1 mol of the alcohol compound represented by formula (3) .
  • These condensing agents or bases are appropriately selected depending on the kind of the carboxylic acid compound represented by formula (4) or a reactive derivative thereof.
  • the reaction mixture is usually subjected to work-up procedures, for example, the reaction mixture is filtered and then the filtrate is concentrated, or the reaction mixture is poured into water and the resulting solution is extracted with an organic solvent and then the organic layer is concentrated, and the compound of the present invention can be thus obtained.
  • the obtained compound of the present invention can be purified by an operation such as chromatography and distillation .
  • the alcohol compound represented by formula (3) is a commercially available product, or a compound described in JP-A-05-255271, JP-A-57-158765, and can be thus purchased as a commercially available product, or can be produced according to the process described in these publications.
  • An intermediate of the present invention can be produced, for example, by the process shown below. [0032]
  • the carboxylic acid compound represented by . formula (4) can be produced, for example, by the process shown below.
  • R represents C1-C5 alkyl group, and the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a trans configuration
  • R and R 3 represent the same meanings as defined above respectively, and the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a trans configuration
  • R 3 represents the same meanings as defined above, and the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a trans configuration.
  • the reaction is usually conducted by using the phosphonate compound represented by formula (6) in the proportion within the range of the proportion of 1.0 to 1.5 mol and a base in the proportion of within the range of 1 to 10 mol, based on 1 mol of the caronaldehyde ester derivative represented by formula (5), and reacting them in a polar solvent or a non-polar solvent at the range from 0°C to 80°C, and preferably from 0°C to 30°C and thus a compound represented by formula (7) can be obtained.
  • Examples of the base used in the reaction include an alkali metal compounds such as sodium methylate and potassium t- butoxide, metal hydride compounds such as sodium hydride and potassium hydride, and alkali amide compounds such as sodium bis (trimethylsilyl ) amide, lithium bis (trimethylsilyl ) amide and lithium diisopropylamide.
  • alkali metal compounds such as sodium methylate and potassium t- butoxide
  • metal hydride compounds such as sodium hydride and potassium hydride
  • alkali amide compounds such as sodium bis (trimethylsilyl ) amide, lithium bis (trimethylsilyl ) amide and lithium diisopropylamide.
  • Examples of the polar solvent used in the reaction include ethers such as diethyl ether and tetrahydrofuran, acid amides such as N, -dimethylformaldehyde, and sulfoxides such as dimethyl sulfoxide.
  • Examples of the non-polar solvent used in the reaction include hydrocarbons such as benzene, toluene and hexane.
  • reaction mixture After the completion of the reaction, the reaction mixture is subjected to work-up procedures, for example, the reaction mixture is added to water and the resulting solution is extracted with an organic solvent, and then the organic layer is dried and concentrated, and thus the compound represented by formula (7) can be obtained.
  • the reaction is usually conducted by using a base in the proportion within the range from 1 to 10 mol based on 1 mol of the compound represented by formula (7) and then reacting them in a solvent at the range from 0°C to 80°C, and- preferably from 0°C to 30°C and thus a carboxylic acid compound represented by formula (4) can be obtained.
  • a base in the proportion within the range from 1 to 10 mol based on 1 mol of the compound represented by formula (7) and then reacting them in a solvent at the range from 0°C to 80°C, and- preferably from 0°C to 30°C and thus a carboxylic acid compound represented by formula (4) can be obtained.
  • the base used in the reaction include an alkali metal compounds such as potassium hydroxide and sodium hydroxide.
  • solvent used in the reaction examples include ethers such as 1,4-dioxane, tetrahydrofuran, ethyleneglycoldimethylether, alcohols such as methanol, ethanol, propanol, and water and a mixture of these solvents.
  • the reaction mixture is subjected to work-up procedures, for example, the reaction solution is acidified and then extracted with an organic solvent, and then the organic layer is dried and concentrated, and then the carboxylic acid compound represented by formula (4) can be obtained.
  • the caronaldehyde ester derivative represented by formula (5) can be produced according to the process described in Tetrahedron 45, 3039-3052 (1989).
  • Examples of pests on which the compound of the present invention has a control effect include harmful arthropod pests such as harmful insects and harmful acarines, and more specifically, the following pests.
  • Hemiptera Planthoppers (such as Laodelphax striatellus, Nilaparvata lugens, and Sogatella furcifera) , Leafhoppers (such as Nephotettix cincticeps, and Nephotettix virescens) , Aphids (such as Aphis gossypii , and Myzus persicae) , Plant bugs (such as Nezara antennata, Riptortus clavetus, Eysarcoris lewisi, Eysarcoris parvus, Plautia stali, and Halyomorpha mista) ,.
  • Leafhoppers such as Nephotettix cincticeps, and Nephotettix virescens
  • Aphids such as Aphis gossypii , and Myzus persicae
  • Plant bugs such as Nezara antennata, Riptortus clav
  • White flies such as Trialeurodes vaporariorum, Bemisia tabaci, and Bemisia argentifolii
  • Scales such as Aonidiella aurantii, Comstockaspis perniciosa , Unaspis citri, Ceroplastes rubens, and Icerya purchasi
  • Lace bugs such as Cimex lectularius
  • Bed bugs such as Cimex lectularius
  • Lepidoptera Pyralidae (such as Chilo suppressalis, Cnaphalocrocis medinalis, Notarcha derogata, and Plodia interpunctella) , Spodoptera litura, Pseudaletia separata, Noctuidae such as ⁇ Trichoplusia spp., Heliothis spp., and Earias spp.), Pieridae (such as Pieris rapae) , Tortricidae (such as Adoxopheys spp., Grapholita molesta, Adoxophyes orana fasciata , and Cydia pomonella) , Carposinidae (such as Carposina niponensis) , Lyonetiidae (such as Lyonetia spp.), Lymantriidae (such as Lymantria spp.), Lymantriidae (such as Euproct
  • Culex spp. such as Culex pipiens pallens, Culex tritaeniorhynchus, and Culex quinquefasciatus
  • Aedes spp. such . as Aedes aegypti, and Aedes ⁇ albopictus
  • Diabrotica spp. such as Diabrotica virgifera virgifera, and Diabrotica undecimpunctata howardi
  • Scarabaeidae such as Anomala cuprea, and Anomala rufocuprea
  • Curculionidae such as Sitophilus zeamais, Lissorhoptrus oryzophilus, and Callosobruchuys Kunststoffensis
  • Tenebrionidae such as Tenebrio molitor, and Tribolium castaneum
  • Chrysomelidae such as Oulema oryzae, Aulacophora femoralis, Phyllotreta striolata , and Leptinotarsa decemlineata
  • Dermestidae such as Dermestes maculates
  • Anobiidae Epilachna spp.
  • Blattodea Blattella germanica, Periplaneta fuliginosa, Periplaneta americana , Periplaneta brunnea, Blatta orientalis, and so on;
  • Thysanoptera Thrips palmi, Thrips tabaci, Frankliniella occidentalis, Frankliniella intonsa, and so on;
  • Hymenoptera Formicidae (such as Monomorium pharaosis, Formica fusca japonica , Qchetellus glaber, Pristomyrmex ponnes, Pheidole noda, and Linepithema humile) , Long- legged wasps (such as Polistes chinensis antennalis, Polistes jadwigae, and Polistes rothneyi) , Vespidae (such as Vespa mandarinia japonica, Vespa simillima , Vespa analis insularis , Vespa crabro flavofasciata, and Vespa ducalis) , Bethylidae, Xylocopa, Pompilidae, Sphecoidae, Mason wasp, and so on;
  • Formicidae such as Monomorium pharaosis, Formica fusca japonica , Qchetellus glaber, Pristomyrm
  • Orthoptera Mole crickets, Grasshoppers, etc.
  • Shiphonaptera Ctenocephalides felis, Ctenocephalides canis, Pulex irritans, Xenopsylla cheopis, and so on;
  • Anoplura Pediculus humanus corporis, Phthirus pubis, Haematopinus eurysternus, Dalmalinia ovis, and so on;
  • Reticulitermes spp. such as Reticulitermes speratus, Coptotermes formosanus, Reticulitermes flavipes, Reticulitermes hesperus, Reticulitermes virginicus, Reticulitermes tibialis, and Heterotermes aureus
  • Incisitermes spp. such as Incisitermes minor
  • Zootermopsis spp. such as Zootermopsis nevadensis
  • Acarina Tetranychidae (such as Tetranychus urticae, Tetranychus kanzawai , Panonychus citri, Panonychus ulmi, and Oligonychus spp.), Eriophyidae (such as Aculops pelekassi, and Aculus Fuendali) , Tarsonemidae (such as Polyphagotarsonemus latus) , Tenuipalpidae, Tuckerellidae, Ixodxdae (such as Haemaphysalis longicornis, Haemaphysalis flava, Dermacentor variabilis, Ixodes ovatus, Ixodes persulcatus, Ixodes scapularis, Boophilus microplus, Amblyomma americanum, and Rhipicephalus sanguineus) , Acaridae (such as Tyrophagus putrescentiae) , Dermanyssidae (
  • Araneae Japanese foliage spider (Chiracanthium japonicum) , redback spider (Latrodectus hasseltii) , Nephila clavata (Tetragnathidae) , Cyclosa octotuberculata , St.
  • Andrew's cross spider ⁇ Argiope amoena) Wasp spider (Argiope bruennichii) , Orb-weaving spider ⁇ Araneus ventricosus) , Grass spider (Agelena silvatica) , Wolf spider ⁇ Pardosa astrigera) , Dock spider (Dolomedes sulfurous) , Pardosa astrigera, Dolomedes sulfureus, Carrhotus xanthogramma , Common house spider (Achaearanea tepidariorum) , Coelotes insidiosus, Jumping spider (Salticidae) , Huntsman spider ⁇ Heteropoda venatoria) , etc.;
  • Chilopoda Centipedes (such as House centipede ( Thereuonema hilgendorfi) , Scolopendra subspinipes, Scolopendra subspinipes japonica, Scolopocryptops rubiginosus, Bothropolys asperatus, etc.);
  • Diplopoda Millipedes (such as Garden millipede
  • Isopoda Sow bugs (such as Porcellionides pruinosus
  • Pill bugs such as Common pill bug ⁇ Armadillidium vulgare
  • Sea louses such as Wharf roach ⁇ Ligia exotica
  • Gastropoda Tree slug (Limax marginatus), and Yellow slug (Limax flavus), etc.
  • the pest control agent of the present invention is a pest control agent of the present invention.
  • the pest control agent of the present invention is usually formulated into formulations described below.
  • the formulation include an oil solution, an emulsifiable concentrate, a wettable powder, a flowable formulation (e.g., an aqueous suspension, or an aqueous emulsion) , a microcapsule, a dust, a granule, an aerosol, a carbon dioxide formulation, a heat transpiration
  • formulation e.g., an insecticidal coil, an electric
  • insecticidal mat or a liquid absorbing core-type heat transpiration pesticide
  • piezo insecticidal formulation e.g., a heat fumigant (e.g., a self combustion-type fumigant, a chemical reaction-type fumigant, or a porous ceramic plate fumigant), an unheated transpiration formulation (e.g., a resin transpiration formulation, a paper transpiration formulation, an unwoven fabric transpiration formulation, a knit fabric transpiration formulation, or a sublimating tablet), an aerosol formulation (e.g., a fogging
  • a heat fumigant e.g., a self combustion-type fumigant, a chemical reaction-type fumigant, or a porous ceramic plate fumigant
  • an unheated transpiration formulation e.g., a resin transpiration formulation, a paper transpiration formulation, an unwoven fabric transpiration formulation, a knit fabric transpiration formulation, or a sublimating tablet
  • aerosol formulation e.g., a fogging
  • a direct contact formulation e.g., a sheet- shaped contact formulation, a tape-shaped contact
  • Examples of a method of formulation include the following methods.
  • a method comprising mixing the compound of the present invention with a solid carrier, a liquid carrier, a gaseous carrier, a bait or the like, followed by if necessary, addition of a surfactant and other auxiliary agents for formulation, and processing.
  • a method comprising mixing the compound of the present invention and a base material, followed by subjecting the mixture to mold processing.
  • formulations usually contain 0.001 to 98% by weight of the compound of the present invention, depending on formulation forms.
  • inert carrier used in the formulation examples include an inert solid carrier, an inert liquid carrier and an inert gaseous carrier.
  • the solid carrier used in the formulation examples include fine powders or granules of clays (e.g., kaolin clay, diatomaceous earth, bentonite, Fubasami clay, or acid white clay) , synthetic hydrated silicon oxide, talc, ceramics, other inorganic minerals (e.g., sericite, quartz, sulfur, active carbon, calcium carbonate, or hydrated silica), or chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium chloride, or urea) and so on; substances that are in solid form at room temperature (e.g., 2 , , 6-triisopropyl-l , 3 , 5-trioxane, naphthalene, p-dichlorobenzene, camphor, or adamantane) ; as well as felt, fiber, fabric, knit, sheet, paper, thread, foam, porous material and multifilament comprising one or more
  • synthetic resins e.g., polyethylene resins such as low density polyethylene, straight chain low density polyethylene and high density polyethylene;
  • ethylene-vinyl ester copolymers such as an ethylene-vinyl acetate copolymer
  • ethylene-methacrylate copolymers such as an ethylene-methyl methacrylate copolymer and an ethylene-ethyl methacrylate copolymer
  • ethylene-acrylate copolymers such as an ethylene-methyl acrylate copolymer and an ethylene-ethyl acrylate copolymer
  • an ethylene-vinylcarboxylic acid copolymers such as an ethylene-acrylic acid copolymer
  • ethylene-tetracyclododecene copolymers polypropylene resins such as a propylene homopolymer and a propylene- ethylene copolymer; poly-4-methylpentene-l , polybutene-1 , polybutadiene, polystyrene; acrylonitrile-styrene resin; acrylonitrile-butadiene-styrene resins; styrene elastomers such as a styrene-conj
  • liquid carrier examples include aromatic or aliphatic hydrocarbons (e.g., xylene, toluene, alkylnaphthalene, phenylxylylethane , kerosene, light oil, hexane, or cyclohexane) , halogenated hydrocarbons (e.g., chlorobenzene , dichloromethane , dichloroethane , or trichloroethane) , alcohols (e.g., methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, or ethylene glycol), ethers (e.g., diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran, or dioxane) , esters
  • ketones e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone
  • nitriles e.g., acetonitrile, or isobutyronitrile
  • sulfoxides e.g., dimethyl sulfoxide
  • acid amides e.g., N, N-dimethylformamide, N,N- dimethylacetamide, or N-methyl-pyrrolidone
  • alkylidene carbonate e.g., propylene carbonate
  • vegetable oils e.g., soybean. oil, or cottonseed oil
  • plant essential oils e.g., orange oil, hyssop oil, or lemon oil
  • gaseous carrier examples include butane gas, chlorofluorocarbon, liquefied petroleum gas (LPG) , dimethyl ether and carbon dioxide.
  • LPG liquefied petroleum gas
  • surfactant examples include alkyl sulfate, alkyl sulfonate, alkylaryl sulfonate, alkylaryl ethers, polyoxyethylenated alkylaryl ethers, polyethylene glycol ethers, polyhydric alcohol esters and sugar alcohol derivatives .
  • auxiliary agents for formulation examples include a binder, a dispersant and a stabilizer.
  • specific examples include casein, gelatin, polysaccharides (e.g., starch, gum arabic, cellulose derivatives, or alginic acid) , lignin derivatives, bentonite, saccharides, synthetic water-soluble polymers (e.g., polyvinyl alcohol, or polyvinyl pyrrolidone) , polyacrylic acid, BHT ( 2 , 6-di-tert- butyl-4-methylphenol) and BHA (a mixture of 2-tert-butyl-4- methoxyphenol and 3-tert-butyl-4-methoxyphenol) .
  • BHT 2-tert-butyl-4- methoxyphenol and 3-tert-butyl-4-methoxyphenol
  • Examples of a base material for the insecticidal coil include a mixture of vegetable powder such as wood flour and lees powder, and a binder such as incense material powder, starch and gluten.
  • Examples of a base material for the electric insecticidal mat include a plate obtained by hardening cotton linter and a plate obtained by hardening fibrils of a mixture of cotton linter and pulp.
  • Examples of a base material for the self combustion- type fumigant include combustible exothermic agents such as nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethylcellulose and wood flour; thermal decomposition stimulants such as alkali metal salt, alkaline earth metal salt, dichromate and chromate; oxygen carriers such as potassium nitrate; combustion-supporting agents such as melamine and flour starch; extenders such as diatomaceous earth, and binders such as synthetic glue.
  • combustible exothermic agents such as nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethylcellulose and wood flour
  • thermal decomposition stimulants such as alkali metal salt, alkaline earth metal salt, dichromate and chromate
  • oxygen carriers such as potassium nitrate
  • combustion-supporting agents such as melamine and flour starch
  • extenders such as diatomaceous earth, and binders
  • Examples of a base material for the chemical reaction- type fumigant include exothermic agents such as alkali metal sulfide, polysulfide, hydrosulfide and calcium oxide; catalytic agents such as a carbonaceous material, iron carbide and active white clay; organic foaming agents such as azodicarbonamide, benzenesulfonylhydrazide , dinitropentamethylenetetramine, polystyrene and polyurethane; and fillers such as strips of natural fiber and synthetic fiber.
  • exothermic agents such as alkali metal sulfide, polysulfide, hydrosulfide and calcium oxide
  • catalytic agents such as a carbonaceous material, iron carbide and active white clay
  • organic foaming agents such as azodicarbonamide, benzenesulfonylhydrazide , dinitropentamethylenetetramine, polystyrene and polyurethane
  • fillers such as strips of natural fiber and synthetic fiber.
  • Examples of a resin used as a base material of the resin transpiration formulation include polyethylene resins such as a low density polyethylene, a straight chain low density polyethylene and a high density polyethylene; ethylene-vinyl ester copolymers such as an ethylene-vinyl acetate copolymer; ethylene-methacrylate copolymers such as an ethylene-methyl methacrylate copolymer and an ethylene- ethyl methacrylate copolymer; ethylene-acrylate copolymers such as an ethylene-methyl acrylate copolymer and an ethylene-ethyl acrylate copolymer; ethylene-vinylcarboxylic acid copolymers such as an ethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymers; polypropylene resins such as a propylene copolymer and a propylene- ethylene copolymer; poly-4-methylpentene-l , polybuten
  • the base materials may be used alone or as a combination of two or more kinds. If necessary, a plasticizer such as phthalate esters (e.g., dimethyl phthalate, dioctyl phthalate, etc.), adipic acid esters and stearic acid may be added to these base materials.
  • the resin transpiration formulation can be prepared by mixing the compound of the present invention with the above-mentioned base material, kneading the mixture, followed by molding it by injection molding, extrusion molding or pressure molding. The resultant resin formulation can be subjected to further molding or cutting procedure, if necessary, to be processed into shapes such as a plate, film, tape, net or string shape. These resin formulations can be processed into animal collars, animal ear tags, sheet products, trap strings, gardening supports and other products.
  • Examples of a base material for the poison bait include bait ingredients such as grain powder, vegetable oil, saccharide and crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, accidental ingestion inhibitors for children and pets such as a chili powder; insect attraction fragrances such as cheese flavor, onion flavor and peanut oil.
  • bait ingredients such as grain powder, vegetable oil, saccharide and crystalline cellulose
  • antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid
  • preservatives such as dehydroacetic acid
  • accidental ingestion inhibitors for children and pets such as a chili powder
  • insect attraction fragrances such as cheese flavor, onion flavor and peanut oil.
  • the pest control method of the present invention is usually conducted by applying an effective amount of the compound of the present invention to a pest or a habitat thereof (e.g. plant bodies, soil, the interior of a house, animal bodies, the interior of a car, or outdoor open space) in the form of a pest control agent of the present invention.
  • a pest or a habitat thereof e.g. plant bodies, soil, the interior of a house, animal bodies, the interior of a car, or outdoor open space
  • a method for applying the pest control agent of the present invention includes the following methods, and is appropriately selected depending on the form of the pest control agent of the present invention, the application area and so on.
  • a method comprising diluting a pest control agent of the present invention with a solvent such as water, and then spraying the dilution to a pest or a habitat of the pest .
  • the pest control agent of the present invention is usually formulated into an emulsifiable concentrate, a wettable powder, a flowable formulation, a microcapsule or the like.
  • the formulation is usually diluted so that the concentration of the compound of the present invention can be within the range from 0.1 to 10,000 ppm.
  • a method comprising heating a pest control agent of the present invention at a habitat of a pest, thereby allowing an active ingredient to volatilize and diffuse from the pest control agent.
  • any of the amount and concentration of application of the compound of the present invention can be appropriately determined depending on the form, application period, application area or application method of the pest control agent of the present invention, or kind of a pest, damage to be incurred and so on.
  • the amount to be applied is usually from within the range from 0.0001 to 1,000 mg/m 3 of the compound of the present invention in the case of applying to a space, and within the range from 0.0001 to 1, 000 mg/m 2 of the compound of the present invention in the case of applying to a plane.
  • An insecticidal coil or an electric insecticidal mat and so on is applied by heating to volatilize and diffuse an active ingredient, depending on the form of the formulation.
  • a resin transpiration formulation, a paper transpiration formulation, an unwoven fabric transpiration formulation, a knit fabric transpiration formulation or a sublimating tablet and so on are allowed to stand as it is in a space to be applied, and place under air blowing.
  • the pest control agent of the present invention When the pest control agent of the present invention is applied to a space for the purpose of prevention of epidemics, examples of the space include a closet, a Japanese cabinet, a Japanese chest, a cupboard, a toilet, a bathroom, a shed, a living room, a dining room, a garage, the interior of a car and so on.
  • the pest control agent can be also applied to outdoor open space.
  • the pest control agent of the present invention When the pest control agent of the present invention is used for controlling external parasites of livestock such as cows, horses, pigs, sheep, goats and chickens and small animals such as dogs, cats, rats and mice, the pest control agent of the present invention can be applied to the animals by a known method in the veterinary field. Specifically, when systemic control is intended, the pest control agent of the present invention is administered to the animals as a tablet, a mixture with feed or a suppository, or by injection (including intramuscular, subcutaneous, intravenous and intraperitoneal injections).
  • the pest control agent of the present invention is applied to the animals by means of spraying of the oil solution or aqueous solution, pour-on or spot-on treatment, or washing of the animal with a shampoo formulation, or by putting a collar or ear tag made of the resin transpiration formulation to the animal.
  • the dosage of the compound of the present invention is usually within the range from 0.01 to 1,000 mg per 1 kg of an animal body weight.
  • examples of the application method include a spray treatment, a soil treatment, a seed treatment and a submerged treatment.
  • the amount can widely vary depending on the application period, application area, application method and other factors, and is usually within the range from 1 to 10,000 g in terms of the compound of the present invention per 10, 000 m 2 .
  • the pest control agent of the present invention is formulated into an emulsifiable concentrate, a wettable powder, a flowable formulation and so on, the pest control agent is usually applied after diluting with water so that the concentration of the active ingredient becomes a range from 0.01 to 10,000 ppm, and a granule or a dust is usually applied as it is.
  • formulations or water dilutions of the formulations may be directly sprayed over pests or plants such as crop plants to be protected from pests, or may be used in the soil treatment for the control of pests which inhabit the soil of the cultivated land.
  • Application can also be conducted by a method of directly winding the resin formulation formed into sheet- shaped, or string- or cord-shaped formulation around plants, disposing the formulation in the neighborhood of plants, or spreading the formulation on the soil surface at the root.
  • the compound of the present invention can be used as pest control agent in cultivating field such as farm, paddy field, lawn or orchard, or non-cultivating field.
  • the compound of the present invention can control pests which inhabit the cultivating field in the cultivating field and so on where the following "plant crops" are cultivated.
  • Agricultural crops corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, sarrazin, sugar beet, rapeseed, sunflower, sugar cane, tobacco, etc.;
  • Vegetables Solanaceae vegetables (eggplant, tomato, green pepper, hot pepper, potato etc.), Cucurbitaceae vegetables (cucumber, pumpkin, zucchini, watermelon, melon etc.), Cruciferae vegetables (Japanese radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, brown mustard, broccoli, cauliflower etc.), Compositae vegetables (burdock, garland chrysanthemum, artichoke, lettuce etc.), Liliaceae vegetables (Welsh onion, onion, garlic, asparagus etc.), Umbelliferae vegetables (carrot, parsley, celery, parsnip etc.), Chenopodiaceae vegetables (spinach, Swiss chard etc.), Labiatae vegetables (Japanese basil, mint, basil etc.), strawberry, sweat potato, yam, aroid, etc.;
  • Fruit trees pomaceous fruits (apple, common pear, Japanese pear, Chinese quince, quince etc.), stone fleshy fruits (peach, plum, nectarine, Japanese plum, cherry, apricot, prune etc.); citrus plants (Satsuma mandarin, orange, lemon, lime, grapefruit etc.), nuts (chestnut, walnut, hazel nut, almond, pistachio, cashew nut, macadamia nut etc.), berry fruits (blueberry, cranberry, blackberry, raspberry etc.), grape, persimmon, olive, loquat, banana, coffee, date, coconut palm, oil palm, etc.;
  • Trees other than fruit trees tea, mulberry, woody plants (azalea, camellia, hydrangea, sasanqua, Illicium religiosum, cherry tree, tulip tree, crape myrtle, fragrant olive etc.), street trees (ash tree, birch, dogwood, eucalyptus, ginkgo, lilac, maple tree, oak, poplar, cercis, Chinese sweet gum, plane tree, zelkova, Japanese arborvitae, fir tree, Japanese hemlock, needle juniper, pine, spruce, yew, elm, horse-chestnut etc.), sweet viburnum, Podocarpus macrophyllus , Japanese cedar, Japanese cypress, croton, spindle tree, Chinease howthorn, etc.
  • flowers (rose, carnation, chrysanthemum, Eustoma grandiflorum Shinners (prairie gentian) , gypsophila, gerbera, pot marigold, salvia, petunia, verbena, tulip, aster, gentian, lily, pansy, cyclamen, orchid, lily of the valley, lavender, stock, ornamental kale, primula, poinsttia gladiolus, cattleya, daisy, verbena, cymbidium, begonia, etc.), bio-fuel plants (Jatropha, safflower, gold- of-pleasure, switchgrass, Miscanthus, ribbon grass, giant reed, kenaf, cassava, willow, etc.), foliage plant; etc.
  • plant crops include gene transgenic plant crops.
  • the compound of the present invention can be mixed with or can be used in combination with other insecticide, acaricide, nematocide, soil pest control agent, fungicide, herbicide, plant growth regulating agent, repellent, synergist, fertilizer, or soil modifier.
  • active ingredient of such the insecticide and acaricide examples include:
  • acrinathrin allethrin, beta-cyfluthrin, bifenthrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, empenthrin, deltamethrin, esfenvalerate, ethofenprox, fenpropathrin, fenvalerate, flucythrinate, flufenoprox, flumethrin, fluvalinate, halfenprox, imiprothrin, permethrin, prallethrin, pyrethrins, resmethrin, sigma- cypermethrin, silafluofen, tefluthrin, .
  • tralomethrin transfluthrin, tetramethrin, phenothrin, cyphenothrin, alpha-cypermethrin, zeta-cypermethrin, lambda-cyhalothrin, gamma-cyhalothrin, furamethrin, tau-fluvalinate , metofluthrin, 2, 3, 5, 6-tetrafluoro-4-methylbenzyl 2,2- dimethyl-3- ( 1-propenyl ) cyclopropane carboxylate, 2,3,5,6- tetrafluoro-4- (methoxymethyl) benzyl 2, 2-dimethyl-3- (2- methyl-l-propenyl ) cyclopropane carboxylate, 2,3,5,6- tetrafluoro-4- (methoxymethyl) benzyl 2,2,3,3- tetramethylcyclopropane carboxylate, and so on;
  • acephate Aluminium phosphide, butathiofos, cadusafos, chlorethoxyfos , chlorfenvinphos , chlorpyrifos , chlorpyrifos-methyl , cyanophos (abbrev. CYAP) , diazinon, DCIP (dichlorodiisopropyl ether) , dichlofenthion (abbrev. ECP) , dichlorvos (abbrev. DDVP) , dimethoate, dimethylvinphos , disulfoton, EPN, ethion, ethoprophos, etrimfos, fenthion (abbrev.
  • PAP profenofos, propaphos, prothiofos, pyraclorfos, salithion, sulprofos, tebupirimfos , temephos, tetrachlorvinphos, terbufos, thiometon, trichlorphon (abbrev. DEP) , vamidothion, phorate, cadusafos, and so on;
  • cartap bensultap, thiocyclam, monosultap, bisultap, and so on;
  • chlorfluazuron bistrifluron, diafenthiuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron , lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron, triazuron, and so on;
  • chromafenozide chromafenozide, halofenozide, methoxyfenozide, tebufenozide, and so on;
  • aldrin dieldrin, dienochlor, endosulfan, methoxychlor, and so on;
  • avermectin-B bromopropylate, buprofezin,
  • chlorphenapyr cyromazine, D-D (1, 3-Dichloropropene) , emamectin-benzoate, fenazaquin, flupyrazofos , hydroprene, methoprene, indoxacarb, metoxadiazone, milbemycin-A, pymetrozine, pyridalyl, pyriproxyfen, spinosad, sulfluramid, tolfenpyrad, triazamate, flubendiamide, lepimectin, Arsenic acid, benclothiaz, Calcium cyanamide, Calcium polysulfide, chlordane, DDT, DSP, flufenerim, flonicamid, flurimfen, formetanate, metam-ammonium, metam-sodium, Methyl bromide, Potassium oleate, protrifenbute, spiromesifen, Sulfur, metaflumizone
  • Examples of the active ingredient of the repellent include N, N-diethyl-m-toluamide , limonene, linalool, citronellal, menthol, menthone, hinokitiol, geraniol, eucalyptol, indoxacarb, carane-3, 4-diol, MGK-R-326, MGK-R- 874 and BAY-KBR-3023.
  • Examples of the active ingredient of the synergist include 5- [2- (2-butoxyethoxy) ethoxymethyl ] -6-propyl-l, 3- benzodioxol, N- ( 2-ethylhexyl ) bicyclo [ 2.2.1 ] hept-5-ene-2 , 3- dicarboxyimide, octachlorodipropylether, thiocyanoacetic acid isobornyl, and N- (2-ethylhexyl ) -l-isopropyl-4- methylbicyclo [2.2.2] oct-5-ene-2 , 3-dica boxyimide .
  • R 3 represents the same meanings as defined above, is described below.
  • the compound represented by formula (6) wherein R 3 represents methyl group, that is, diethyl methoxy ( cyano) methylphosphonate is synthesized according to the process described in J. Org. Chem. (1976), vol.41, pp .2846-2849.
  • the phosphonate compounds represented by formula (6) wherein R 3 represents ethyl group, propyl group or isopropyl group that is, diethyl ethoxy (cyano) methylphosphonate, diethyl propoxy (cyano)methylphosponate, or diethyl isopropoxy (cyano) methylphosphonate is similarly synthesized according to the process described in J. Org. Chem. (1976) vol.41, pp.2846-2849, except that ethoxyacetonitrile, propoxyacetonitrile or isopropoxyacetonitrile is used in place of methoxyacetonitrile .
  • SORPOL 3005X Five (5) parts of SORPOL 3005X is added to 40 parts of each of the compounds (1) to (8) of the present invention and the mixture is thoroughly mixed, and 32 parts of CARPLEX #80 (synthetic hydrated silicon oxide, a registered trademark of SHIONOGI & CO., LTD.) and 23 parts of 300-mesh diatomaceous earth are added thereto, followed by mixing with stirring by a mixer to obtain wettable powders.
  • CARPLEX #80 synthetic hydrated silicon oxide, a registered trademark of SHIONOGI & CO., LTD.
  • a clay (kaoline clay, manufactured by Shoukouzan Kougyousho) is thoroughly pulverized and mixed, and water is added thereto. The mixture is thoroughly kneaded, granulated by an extruding granulator, and then dried to obtain 1.5 % . granules.
  • xanthan gum and 1.0 part of VEEGUM R aluminum magnesium silicate, manufactured by Sanyo Chemical industries, Ltd.
  • VEEGUM R aluminum magnesium silicate, manufactured by Sanyo Chemical industries, Ltd.
  • a mixture of 10 parts of each of the compounds (1) to (8) of the present invention and 10 parts of phenylxylylethane is added to 20 parts of a 10% aqueous solution of polyethylene glycol, and the mixture is stirred by a homomixer to obtain an emulsion having an average particle diameter of 3 ym.
  • 0.2 part of xanthan gum and 1.0 part of VEEGUM R are dispersed in 58.8 parts of ion-exchanged water to obtain a thickener solution.
  • 40 parts of the above- mentioned emulsion solution and 60 parts of the above- mentioned thickener solution are mixed to obtain flowable formulations.
  • Zero point one (0.1) part of each of the compounds (1) to (8) of the present invention is dissolved in 10 parts of dichloromethane and the solution is mixed with 89.9 parts of deodorized kerosine to obtain oil solutions.
  • Zero point one (0.1) part of each of the compounds (1) to (8) of the present invention and 39.9 parts of deodorized kerosine are mixed and dissolved, and the solution is filled into an aerosol container and a valve portion is installed. Then, 60 parts of power propellant (liquefied petroleum gas) is filled therein under pressure through the valve portion to obtain oil-based aerosol formulations .
  • power propellant liquefied petroleum gas
  • Zero point six (0.6) part of each of the compounds (1) of (8) of the present invention 5 parts of xylene, 3.4 parts of deodorized kerosine and 1 part of Reodol MO-60 (emulsifier, a registered trademark of Kao Corporation) are mixed and dissolved, and then the resulting solution and 50 parts of water are filled into an aerosol container, and then 40 parts of power propellant (liquefied petroleum gas) is filled therein under pressure through a valve portion to obtain aqueous aerosol formulations.
  • power propellant liquefied petroleum gas
  • Zero point three (0.3) g of each of the compounds (1) to (8) of the present invention is dissolved in 20 mL of acetone, and the resulting solution is uniformly mixed with stirring with 99.7 g of a base material for a coil (obtained by mixing Tabu powder, Pyrethrum mark and wooden powder at a ratio of 4:3:3). Then, 100 mL of water is added thereto, and the mixture is thoroughly kneaded, dried and molded to obtain insecticidal coils.
  • a mixture of 0.8 g of each of the compounds (1) to (8) of the present invention and 0.4 g of piperonyl butoxide is dissolved in acetone and the total volume is adjusted to 10 mL. Then, 0.5 mL of this solution is uniformly impregnated into a base material for an insecticidal mat for electric heating (a plate obtained by hardening fibrils of a mixture of cotton linters and pulp) having a size of 2.5 cm ⁇ 1.5 cm and a thickness of 0.3 cm to obtain insecticidal mats for electric heating.
  • a base material for an insecticidal mat for electric heating a plate obtained by hardening fibrils of a mixture of cotton linters and pulp having a size of 2.5 cm ⁇ 1.5 cm and a thickness of 0.3 cm to obtain insecticidal mats for electric heating.
  • a solution obtained by dissolving 3 parts of each of the compounds (1) to (8) of the present invention in 97 parts of deodorized kerosine is poured into a vessel made of vinyl chloride.
  • a liquid absorptive core whose upper part can be heated by a heater an inorganic pulverized powder is hardened with a binder and sintered is inserted thereinto to obtain parts to be used for a liquid absorptive core type thermal transpiring apparatus.
  • One hundred (100) g of each of the compounds (1) to (8) of the present invention is dissolved in an appropriate amount of acetone, and the resulting solution is. uniformly applied to filter paper having a size of 2 cm * 2 cm and a thickness of 0.3 mm, and air-dried to remove acetone, and thus volatile agents for using at room temperature are obtained .
  • Test Examples illustrate that the compounds of the present invention are effective as an active ingredient of a pest control agent.
  • Knocked-down ratio (%) (Number of knocked-down cockroaches / Number of test cockroaches) ⁇ 100
  • each 0.00625 part of each of the compounds (1) to (8) of the present invention was dissolved in 10 parts of isopropyl alcohol, and the resulting solution was mixed with 89.99375 parts of deodorized kerosene to prepare a 0.00625% (w/v) oil solution.
  • Knocked-down ratio (%) (Number of knocked-down cockroaches / Number of test cockroaches) * 100
  • each 0.1 part of each of the compounds (1) to (8) of the present invention was dissolved in 10 parts of isopropyl alcohol, and the resulting solution was mixed with 89.9 parts of deodorized kerosene to prepare a 0.1% (w/v) oil solution.
  • Knocked-down ratio (%) (Number of knocked-down cockroaches / Number of test cockroaches) * 100
  • Each 0.00625 part of each of the compounds (1) to (7) of the, present invention was dissolved in 10 parts of isopropyl alcohol, and the resulting solution was mixed with 89.99375 parts of deodorized kerosene to prepare a 0.00625 part (w/v) oil solution.
  • the compound of the present invention has an excellent pest control effect and is therefore useful as active ingredient of a pest control agent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (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)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Composé ester représenté par la formule (1) dans laquelle Q représente N(CH2C≡CH)-CH2-C*(=O) ou N(CH2C≡CH)-C(CH3)=N* (dans laquelle * représente une position de liaison avec un atome de N adjacent à un groupe carbonyle) ; R3 représente un groupe alkyle C1-C4 ; et une configuration relative entre le substituant à la position 1 du cycle cyclopropane et le substituant à la position 3 du cycle cyclopropane est une configuration trans. Ledit composé possède un excellent effet de lutte contre les ennemis des cultures.
PCT/JP2012/071937 2011-08-24 2012-08-23 Composé ester et son utilisation WO2013027864A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4176189A (en) * 1977-06-20 1979-11-27 Sumitomo Chemical Company, Limited Insecticidal and acaricidal hydantoin N-methylol esters
JPS57158765A (en) 1981-03-24 1982-09-30 Sumitomo Chem Co Ltd Carboxylic acid ester, its preparation, and insecticide containing said ester as active component
JPS6016962A (ja) 1983-06-14 1985-01-28 ルセル−ユクラフ シアノ基を有するシクロプロパンカルボン酸のエステル，その製造法及びその殺虫殺ダニ剤としての使用
JPH05255271A (ja) 1992-03-10 1993-10-05 Sumitomo Chem Co Ltd ３−ヒドロキシメチル−１−プロパルギルイミダゾリジン−２，４−ジオンの製造法
WO2010087419A2 (fr) * 2009-01-28 2010-08-05 Sumitomo Chemical Company, Limited Composé ester et utilisation de celui-ci
WO2011105523A2 (fr) * 2010-02-25 2011-09-01 Sumitomo Chemical Company, Limited Composé ester et utilisation de celui-ci

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4176189A (en) * 1977-06-20 1979-11-27 Sumitomo Chemical Company, Limited Insecticidal and acaricidal hydantoin N-methylol esters
JPS57158765A (en) 1981-03-24 1982-09-30 Sumitomo Chem Co Ltd Carboxylic acid ester, its preparation, and insecticide containing said ester as active component
JPS6016962A (ja) 1983-06-14 1985-01-28 ルセル−ユクラフ シアノ基を有するシクロプロパンカルボン酸のエステル，その製造法及びその殺虫殺ダニ剤としての使用
US4602038A (en) * 1983-06-14 1986-07-22 Roussel Uclaf Insecticidal cyclopropane carboxylates
JPH05255271A (ja) 1992-03-10 1993-10-05 Sumitomo Chem Co Ltd ３−ヒドロキシメチル−１−プロパルギルイミダゾリジン−２，４−ジオンの製造法
WO2010087419A2 (fr) * 2009-01-28 2010-08-05 Sumitomo Chemical Company, Limited Composé ester et utilisation de celui-ci
WO2011105523A2 (fr) * 2010-02-25 2011-09-01 Sumitomo Chemical Company, Limited Composé ester et utilisation de celui-ci

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"The Second series of pharmaceutical research and development", vol. 18, 1993, HIROKAWA SHOTEN, article "Development of agrochemicals III", pages: 493
J. ORG. CHEM., vol. 41, 1976, pages 2846 - 2849
J. ORG. CHEM., vol. 41, 1976, pages 2846 - 2B49
PESTICIDE SCIENCE, vol. 10, 1979, pages 291
TETRAHEDRON, vol. 45, 1989, pages 3039 - 3052

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TW201328601A (zh) 2013-07-16
CN103781769A (zh) 2014-05-07
CN103781769B (zh) 2015-09-09
JP2013060435A (ja) 2013-04-04

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