Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
  • C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
  • C07C69/747—Chrysanthemumic acid esters

Definitions

• the present invention relates to an ester compound, a pest control agent and a pest control method using the ester compound.
• Patent Documents 1 and 2 disclose certain ester compounds. However, the control efficacy of these disclosed pest control ingredients is not always satisfactory.
• An object of the present invention is to provide a novel ester compound having an excellent pest control effect and a method for controlling pests using the same.
• an ester compound represented by the following general formula [Chemical Formula 1] (I) (hereinafter sometimes referred to as an alkyl-containing ester compound) or a general formula [Chemical Formula 3] (I)
• an ester compound (hereinafter sometimes referred to as a dihalo-containing ester compound) has an excellent pest control effect, and has completed the present invention.
• R 1 represents a hydrogen atom or a methyl group
• R 2 also represents a methyl group
• R 1 represents a hydrogen atom
• R 2 represents the following general formula: ] (II)
• X and Y are the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms.
• R 3 represents a hydrogen atom, trifluoromethyl group, methyl group, methoxy group, methoxymethyl group, allyl group, ethynyl group or propargyl group
• R 4 represents a fluorine atom or a carbon number.
• R 5 when R 4 represents a fluorine atom is an alkyl group having 1 to 4 carbon atoms, also, when R 4 represents an alkyl group having 1 to 4 carbon atoms, R 5 Represents the same alkyl group having 1 to 4 carbon atoms as R 4 .
• the ester compound shown by this. [2] An ester compound in which R 4 is a fluorine atom in [1]. [3] An ester compound in which R 5 is a methyl group or an ethyl group in [2]. [4] An ester compound in which R 5 is a methyl group in [3].
• R 1 represents a hydrogen atom or a methyl group
• R 2 also represents a methyl group
• R 1 represents a hydrogen atom
• R 2 represents the following general formula: ] (II)
• X and Y are the same or different and represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms.
• R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group, or a propargyl group
• R 4 represents a chlorine atom or a bromine atom. Represents.
• the compound of the present invention Since the compound of the present invention has an excellent pesticidal activity, it is useful as an active ingredient of a pesticidal agent.
• R 1 represents a hydrogen atom
• the present invention includes each isomer having pesticidal activity and any ratio of isomer mixtures.
• R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group, or a propargyl group
• R 4 represents a fluorine atom or a carbon number of 1
• It represents 1-4 alkyl groups
• R 1 represents a hydrogen atom or a methyl group
• R 2 also represents a methyl group
• R 1 represents a hydrogen atom
• R 2 represents the following general formula: ] (V)
• X and Y are the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms.
• the compound of the present invention is obtained by reacting with a carboxylic acid compound represented by the formula:
• Examples of the reactive derivative include an acid halide of the carboxylic acid compound represented by the formula [Chem. 6], an acid anhydride of the carboxylic acid compound, and an ester of the carboxylic acid compound.
• Examples of the acid halide include acid chloride compounds, and examples of the ester include methyl ester and ethyl ester.
• the reaction is usually performed in a solvent in the presence of a condensing agent or a base.
• Examples of the condensing agent include dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride
• Examples of the base include organic bases such as triethylamine, pyridine, 4-dimethylaminopyridine, diisopropylethylamine.
• Examples of the solvent include hydrocarbons such as toluene and hexane, ethers such as tetrahydrofuran, esters such as ethyl acetate, halogenated hydrocarbons such as chlorobenzene, and mixed solvents thereof.
• the molar ratio of the alcohol compound represented by the formula [Chemical Formula 5] and the carboxylic acid compound represented by the formula [Chemical Formula 6] or a reactive derivative thereof can be arbitrarily set, but preferably equimolar Or a ratio close to that.
• the condensing agent or base can be used in an arbitrary ratio, usually from 0.25 mol to an excess amount, preferably 0.5 mol with respect to 1 mol of the alcohol compound represented by the formula [Chemical Formula 5]. ⁇ 2 moles.
• These condensing agents or bases are appropriately selected depending on the type of the carboxylic acid compound represented by the formula [Chemical Formula 6] or a reactive derivative thereof.
• the reaction mixture after completion of the reaction is filtered to concentrate the filtrate, or poured into water and then subjected to usual post-treatment operations such as organic solvent extraction and concentration, whereby the compound of the present invention is obtained.
• the obtained compound of the present invention can be purified by operations such as chromatography and distillation.
• R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propargyl group.
• R 4 represents a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and when R 4 represents a fluorine atom, R 5 represents an alkyl group having 1 to 4 carbon atoms, and R 4 represents an alkyl group having 1 to 4 carbon atoms.
• R 5 represents the same alkyl group having 1 to 4 carbon atoms as R 4 ), for example, by the following synthetic route [Chemical Formula 8] (VI) ⁇ (III) Can do.
• the aldehyde compound represented by the general formula (VI) can be produced by reducing the aldehyde compound represented by the general formula (VI). Specifically, it is reacted with a reducing agent (eg, sodium borohydride) in an organic solvent (eg, ethanol, methanol, hexane, toluene, tetrahydrofuran, diethyl ether, etc.) at ⁇ 30 to 20 ° C. for 1 to 10 hours. Can be manufactured.
• a reducing agent eg, sodium borohydride
• organic solvent eg, ethanol, methanol, hexane, toluene, tetrahydrofuran, diethyl ether, etc.
• an aldehyde compound represented by the general formula (VI) (wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propargyl group).
• R 4 represents a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and when R 4 represents a fluorine atom, R 5 represents an alkyl group having 1 to 4 carbon atoms, and R 4 represents an alkyl group having 1 to 4 carbon atoms.
• R 5 represents the same alkyl group having 1 to 4 carbon atoms as R 4 ), for example, the following synthetic route [Chemical Formula 9] (VII) ⁇ (VI) Can do.
• an imine compound represented by the general formula (VII) (wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group, or a propargyl group;
• An alkyl Grignard reagent R 5 MgZ (wherein R 5 is an alkyl having 1 to 4 carbon atoms) in an inert solvent (eg, hexane, toluene, tetrahydrofuran, diethyl ether, etc.).
• Z represents a chlorine atom, a bromine atom or an iodine atom) at ⁇ 30 to 60 ° C. for 1 to 24 hours, and 1N to 12N hydrochloric acid aqueous solution is added to the reaction solution for 30 minutes to It can be produced by further reacting for 2 hours.
• An imine compound represented by the general formula (VII) (wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group, or a propargyl group, and R represents a carbon number) 1 to 5 alkyl groups) can be produced, for example, by the following synthetic route [Chemical Formula 10] (VIII) ⁇ (VII).
• an aldehyde compound represented by the general formula (VIII) (wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxymethyl group, an allyl group, an ethynyl group or a propargyl group) in an organic solvent (for example, it is produced by reacting with a primary amine RNH 2 (R represents an alkyl group having 1 to 5 carbon atoms) at ⁇ 10 to 100 ° C. for 5 minutes to 10 hours in hexane, toluene, tetrahydrofuran, diethyl ether, etc. can do.
• RNH 2 R represents an alkyl group having 1 to 5 carbon atoms
• the carboxylic acid compound represented by the general formula [Chemical Formula 6] or a reactive derivative thereof is a known substance.
• Examples of the compound of the present invention include the following compounds.
• Compound 1 of the present invention 2-methyl-3,5,6-trifluorobenzyl (1RS) -trans, cis-3- (2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate,
• Compound 2 of the present invention 2-methyl-3,5,6-trifluorobenzyl (1R) -trans, cis-3- (2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate,
• Compound 3 of the present invention 2-methyl-3,5,6-trifluorobenzyl (1R) -trans-3- (2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate
• Compound 4 of the present invention 2-methyl-3,5,6-trifluorobenzyl (1R) -trans, cis-3- (2,2-difluoro-1-ethenyl) -2,2-dimethylcyclo
• R 1 represents a hydrogen atom or a methyl group
• R 2 also represents a methyl group
• R 1 represents a hydrogen atom
• R 2 represents the following general formula: ] (V)
• X and Y are the same or different and represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms.
• the compound of the present invention is obtained by reacting with a carboxylic acid compound represented by the formula:
• Examples of the reactive derivative include an acid halide of the carboxylic acid compound represented by the formula (IV), an acid anhydride of the carboxylic acid compound, and an ester of the carboxylic acid compound.
• Examples of the acid halide include acid chloride compounds, and examples of the ester include methyl ester and ethyl ester.
• the reaction is usually performed in a solvent in the presence of a condensing agent or a base.
• Examples of the condensing agent include dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, and examples of the base include triethylamine, pyridine, 4-dimethylaminopyridine, diisopropylethylamine and the like.
• An organic base is mentioned.
• Examples of the solvent include hydrocarbons such as toluene and hexane, ethers such as tetrahydrofuran, esters such as ethyl acetate, halogenated hydrocarbons such as chlorobenzene, and mixed solvents thereof.
• the molar ratio of the alcohol compound represented by the formula (III) and the carboxylic acid compound represented by the formula (IV) or a reactive derivative thereof can be arbitrarily set, but is preferably equimolar or A close ratio.
• the condensing agent or base can be used usually in an arbitrary ratio from 0.25 mol to an excess amount, preferably from 0.5 mol to 1 mol, with respect to 1 mol of the alcohol compound represented by the formula (III). 2 moles.
• These condensing agents or bases are appropriately selected depending on the type of the carboxylic acid compound represented by the formula (IV) or a reactive derivative thereof.
• the reaction mixture after completion of the reaction is filtered to concentrate the filtrate, or poured into water and then subjected to usual post-treatment operations such as organic solvent extraction and concentration, whereby the compound of the present invention is obtained.
• the obtained compound of the present invention can be purified by operations such as chromatography and distillation.
• a carbonyl compound represented by (wherein, R 3 is a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propargyl group, R 4 Represents a chlorine atom or a bromine atom).
• R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propargyl group).
• R 4 represents a chlorine atom or a bromine atom) in an organic solvent (eg, ethanol, methanol, hexane, toluene, tetrahydrofuran, diethyl ether, etc.) and a reducing agent (eg, sodium borohydride, etc.) at ⁇ 30 to 20 It can be produced by reacting at a temperature of 1 to 10 hours.
• organic solvent eg, ethanol, methanol, hexane, toluene, tetrahydrofuran, diethyl ether, etc.
• a reducing agent eg, sodium borohydride, etc.
• the carbonyl compound represented by the general formula (VI) (wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxymethyl group, an allyl group, an ethynyl group, or a propargyl group; 4 represents a chlorine atom or a bromine atom.)
• R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxymethyl group, an allyl group, an ethynyl group, or a propargyl group
• 4 represents a chlorine atom or a bromine atom.
• an epoxide compound represented by the general formula (VII) (wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propargyl group). , R 4 represents a chlorine atom or a bromine atom) and a periodic acid is added at 0 to 20 ° C. and reacted at the same temperature for 1 to 10 hours.
• the epoxide compound represented by the general formula (VII) (wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propargyl group). R 4 represents a chlorine atom or a bromine atom) can be produced, for example, by the following synthetic route [Chemical Formula 16] (VIII) ⁇ (VII).
• Epoxidation includes a method using an organic peracid (for example, metachloroperbenzoic acid, dioxirane, hydrogen peroxide, tertiary butyl hydroperoxide, etc.).
• a compound represented by the general formula (VIII) (wherein R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propargyl group, R 4 represents a chlorine atom or a bromine atom.)
• R 3 represents a hydrogen atom, a trifluoromethyl group, a methyl group, a methoxy group, a methoxymethyl group, an allyl group, an ethynyl group or a propargyl group
• R 4 represents a chlorine atom or a bromine atom.
• the carboxylic acid compound represented by the general formula (IV) or a reactive derivative thereof is a known substance.
• Examples of the compound of the present invention include the following compounds.
• Compound 1 of the present invention 2,6-dichloro-3,5-difluorobenzyl (1RS) -trans, cis-3- (2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate,
• Compound 2 of the present invention 2,6-dichloro-3,5-difluorobenzyl (1R) -trans, cis-3- (2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate, Compound 3 of the present invention; 2,6-dichloro-3,5-difluorobenzyl (1R) -trans-3- (2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate, Compound 4 of the present invention; 2,6-dichloro-3,5-difluorobenzyl (1R) -trans, cis-3- (2,2-diflu
• the pest control agent of the present invention can be used alone as the compound of the present invention (alkyl-containing ester compound, dihalo-containing ester compound) itself, but can also be used as a preparation as described below.
• These preparations include, for example, heat transpiration agents such as mosquito coils, mosquito mats and mosquito collectors, fan mosquito traps, oils, emulsions, aerosols, carbon dioxide preparations, wettable powders, flowables (water suspensions) Suspensions, emulsions in water, etc.), microcapsules, powders, granules, tablets, piezo insecticides, heated smokes (self-burning smoke, chemical reaction smoke, porous ceramic smoke) Agent), non-heated transpiration agent (resin transpiration agent, paper transpiration agent, non-woven fabric transpiration agent, knitted fabric transpiration agent, sublimation tablet, etc.), fumes agent (fogging agent), direct contact agent (sheet-like contact agent, tape form) Contact agents, net-like contact agents, etc.), ULV agents and poison baits.
• heat transpiration agents such as mosquito coils, mosquito mats and mosquito collectors, fan mosquito traps, oils, emulsions, aerosols, carbon dioxide preparations, wettable
• Examples of the formulation method include the following methods. (1) A method in which the compound of the present invention is mixed with a solid carrier, liquid carrier, gaseous carrier, bait and the like, and a surfactant and other formulation adjuvants are added and processed as necessary. (2) A method of impregnating a base material containing no active ingredient with the compound of the present invention. (3) A method of molding after mixing the compound of the present invention and the substrate. These preparations usually contain 0.001 to 98% by weight of the compound of the present invention depending on the preparation form.
• solid carriers used in the formulation include clays (kaolin clay, diatomaceous earth, bentonite, fusami clay, acidic clay), synthetic hydrous silicon oxide, talc, ceramic, and other inorganic minerals (sericite, activated carbon, carbonic acid).
• Fine powders and granules such as calcium, silica, etc., substances which are solid at normal temperature (2,4,6-triisopropyl-1,3,5-trioxane, naphthalene, p-dichlorobenzene, camphor, adamantane, etc.), and Wool, silk, cotton, hemp, pulp, synthetic resin (for example, polyethylene resins such as low density polyethylene, linear low density polyethylene, and high density polyethylene; ethylene-vinyl ester copolymer such as ethylene-vinyl acetate copolymer) Polymer; Ethylene such as ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer -Methacrylic acid ester copolymer; ethylene-acrylic acid ester copolymer such as ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer; ethylene-vinyl carboxylic acid such as ethylene
• liquid carrier examples include aromatic or aliphatic hydrocarbons (xylene, alkylnaphthalene, phenylxylylethane, kerosene, light oil, hexane, cyclohexane, etc.), alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl).
• aromatic or aliphatic hydrocarbons xylene, alkylnaphthalene, phenylxylylethane, kerosene, light oil, hexane, cyclohexane, etc.
• alcohols methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl.
• gaseous carrier examples include compressed gases such as butane gas, Freon gas, liquefied petroleum gas (LPG), dimethyl ether, and carbon dioxide gas.
• compressed gases such as butane gas, Freon gas, liquefied petroleum gas (LPG), dimethyl ether, and carbon dioxide gas.
• Surfactants include, for example, alkyl sulfate esters, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers, polyarylethylenes of alkyl aryl ethers, polyethylene glycol ethers, polyhydric alcohol esters and sugars. Examples include alcohol derivatives.
• formulation adjuvants include fixing agents, dispersants and stabilizers, such as casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, saccharides, Synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone), polyacrylic acid, BHT (2,6-di-tert-butyl-4-methylphenol), and BHA (2-tert-butyl-4-methoxyphenol) And a mixture with 3-tert-butyl-4-methoxyphenol).
• flavor, etc. may be mix
• Examples of the base material of the mosquito coil include a mixture of a vegetable powder such as wood powder and pesticide extracted chrysanthemum powder and a binder such as tab powder, starch, carboxymethylcellulose, and gluten.
• Examples of the base material of the mosquito trap include those obtained by solidifying a cotton linter into a plate shape and those obtained by solidifying a fillet of a mixture of cotton linter and pulp into a plate shape.
• Examples of the base material for the self-combustion type smoke agent include, for example, nitrates, nitrites, guanidine salts, combustion exothermic agents such as potassium chlorate, nitrocellulose, ethylcellulose, and wood flour, heat of alkali metal salts and alkaline earth metal salts. Examples include decomposition stimulants, oxygen supply agents such as potassium nitrate, flame retardants such as melamine and wheat starch, bulking agents such as diatomaceous earth, and binders such as synthetic pastes.
• Examples of the base material for the chemical reaction type smoke agent include exothermic agents such as alkali metal sulfides, polysulfides, hydrosulfides, and calcium oxide, catalyst agents such as iron carbide and activated clay, azodicarbonamide, and benzene.
• examples thereof include organic foaming agents such as sulfonyl hydrazide, dinitropentamethylenetetramine, polystyrene, and polyurethane, and fillers such as natural fiber pieces and synthetic fiber pieces.
• the resin used for the substrate such as a resin transpiration agent
• polyethylene resins such as low density polyethylene, linear low density polyethylene, and high density polyethylene
• ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymers.
• Ethylene-acrylic acid ester copolymer ethylene-vinyl carboxylic acid copolymer such as ethylene-acrylic acid copolymer; polypropylene resin such as polypropylene and propylene-ethylene copolymer; poly-4-methylpentene-1, Polybutene-1, polybutadiene, polystyrene, acrylonitrile Styrene resins; Styrenic elastomers such as acrylonitrile-butadiene-styrene resins, styrene-conjugated diene block copolymers, hydrogenated styrene-conjugated diene block copolymers; fluororesins; acrylic resins such as polymethyl methacrylate; nylon 6, polyamide resins such as nylon 66; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene phthalate; polycarbonate, polyacetal, polyarylate, hydroxybenzoic acid polyester,
• the resin transpiration agent can be obtained by kneading the compound of the present invention in the above-mentioned base material and then molding it by injection molding, extrusion molding, press molding or the like.
• the obtained resin preparation can be further processed into a plate shape, a film shape, a tape shape, a net shape, a string shape or the like through steps such as molding and cutting if necessary.
• These resin preparations are processed, for example, as non-heated transpiration agents, animal collars, animal ear tags, sheet preparations, attracting tapes, attracting strings, horticultural supports, and long-lasting insecticidal nets.
• bait ingredients such as cereal flour, vegetable oil, sugar, crystalline cellulose, antioxidants such as BHT and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, children such as pepper powder and Examples include anti-fouling agents for pets, and pest-attracting perfumes such as cheese flavor, onion flavor, and peanut oil.
• the compound of the present invention can be used in combination with or in combination with other insecticides, acaricides, fungicides, herbicides, repellents, synergists, fertilizers, and soil conditioners.
• Transfluthrin methfluthrin, profluthrin, phenothrin, cyphenothrin, permethrin, cypermethrin (cypermethrin) thrin), cyfluthrin, beta-cyfluthrin, fenpropathrin, bifenthrin, cycloprothrin, deltamethrinthin.
• the active ingredient of the repellent includes, for example, N, N-diethyl-m-toluamide, limonene, linalool, citronellal, menthol, menthone, hinokitiol, geraniol, p-menthane-3,8-diol, eucalyptol, caran-3 , 4-diol, icaridin, IR-3535, MGK-R-326, MGK-R-874, and the like.
• synergist for example, 5- [2- (2-butoxyethoxy) ethoxymethyl] -6-propyl-1,3-benzodioxole, N- (2-ethylhexyl) bicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, octachlorodipropyl ether, isobornyl thiocyanoacetate, N- (2-ethylhexyl) -1-isopropyl-4-methylbicyclo [2.2. 2] Oct-5-ene-2,3-dicarboximide and the like.
• pests for which the compounds of the present invention are effective include harmful arthropods such as harmful insects and harmful mites, and specific examples thereof include the following. Diptera: Culex mosquitoes, Culex mosquitoes, Chikaieka, Aedes mosquitoes, etc., Aedes aegypti, Aedes albopictus, etc.
• Fly flies such as powder flies, seed flies and onion flies, fruit flies, leaf flies, fruit flies, butterflies, fleas, abs, fly flies, sand flies, nucifers, etc .; Reticulate pests: German cockroaches, black cockroaches, American cockroaches, flying cockroaches, cockroaches, etc .; Hymenoptera: ants, wasps, scallops, wasps such as wasps, etc .; Lepidoptera: Inu fleas, cat fleas, human fleas, etc .; Lice eye pests: human lice, white lice, head lice, body lice etc .; Isoptera pests: Yamato termites, termites, etc .; Hemiptera: insects such as Japanese brown planthoppers, leafhoppers, leafhoppers such as leafhoppers, aphids such as cotton aphids, bed bugs such as stink bugs,
• the pest control method of the present invention is carried out by applying an effective amount of the compound of the present invention to a pest or a pest habitat, usually in the form of the pest control agent of the present invention.
• Examples of the method for applying the pest control agent of the present invention include the following methods, which can be appropriately selected depending on the form, place of use, etc. of the pest control agent of the present invention. (1) A method of treating the pest control agent of the present invention as it is in a pest or a habitat of the pest. (2) A method in which the pest control agent of the present invention is diluted with a solvent such as water and then sprayed to a pest or a habitat of the pest.
• the pest control agent of the present invention usually formulated into an emulsion, a wettable powder, a flowable agent, a microcapsule preparation or the like is diluted so that the concentration of the compound of the present invention is 0.1 to 10,000 ppm. .
• both the application amount and the application concentration of the compound of the present invention can be appropriately determined according to the form of the pest control agent of the present invention, the application time, the application place, the application method, the type of the pest, the damage situation, etc. .
• the application amount is usually 0.001 to 100 mg / m 3 as the amount of the compound of the present invention when applied to a space, and 0.001 when applied to a plane. is a ⁇ 100mg / m 2.
• Mosquito coils, mosquito coils, etc. are applied by volatilizing active ingredients by heating according to the form of the formulation.
• Resin transpiration agents, paper transpiration agents, non-woven fabric transpiration agents, knitted fabric transpiration agents, sublimable tablets and the like can be used, for example, by leaving them in the space to be applied as they are and by placing them in the preparation under ventilation.
• Examples of the space to which the pest control composition of the present invention is applied for pest control include living rooms, canteens, bedrooms, closets, closets, Japanese dance, cupboards, toilets, bathhouses, storerooms, warehouses, and the like. It can also be applied in open outdoor spaces.
• the pesticidal composition of the present invention is used for controlling ectoparasites of domestic animals such as cattle, horses, pigs, sheep, goats and chickens, and small animals such as dogs, cats, rats and mice, it is well known in veterinary medicine. Can be used on animals in any way.
• systemic control for example, tablets, mixed feed, suppositories, injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.)
• non-systemic control for example, spraying an oil or aqueous solution, pour-on or spot-on, washing animals with a shampoo formulation, or It is used by a method such as attaching a resin transpiration agent to an animal using a collar or ear tag.
• the amount of the compound of the present invention when administered to an animal body is usually in the range of 0.01 to 100 mg per 1 kg body weight of the animal.
• Production Example 1 Production of Compound (IX) 1-butanamine (0.9 mL, 8) was added to a solution of 2,3,5,6-tetrafluorobenzaldehyde (1.00 g, 5.62 mmol) in toluene (4 mL) under ice cooling. .98 mmol) and p-toluenesulfonic acid monohydrate (11 mg, 0.06 mmol) were sequentially added. After stirring at the same temperature for 1 hour, water was poured into the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and then concentrated under reduced pressure to give the following formula [Chemical Formula 17] (IX)
• Production Example 13 Production of Compound 18 of the Present Invention 2-Methyl-3,5,6-trifluorobenzyl alcohol (40 mg, 0.23 mmol) and (1R) -trans-3-[(E)-(2-methoxycarbonyl) -1-propenyl)]-2,2-dimethylcyclopropanecarboxylic acid (74 mg, 0.35 mmol) in chloroform (3 mL) was added 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (67 mg, 0 .35 mmol) and 4-dimethylaminopyridine (4 mg) were added.
• Production Example 36 Production of Compound 252 of the Present Invention 3,5-difluoro-2,4,6-trimethylbenzyl alcohol (30 mg, 0.16 mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (34 mg, To a chloroform solution (3 mL) of 0.24 mmol) was added 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (46 mg, 0.24 mmol) and 4-dimethylaminopyridine (3 mg). After stirring at room temperature for 26 hours, water was poured into the reaction solution, which was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and then concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain the following formula [Chemical Formula 58] (L)
• Production Example 37 Production of Compound 278 of the present invention 3,5-difluoro-2,6-dimethyl-4-methoxymethylbenzyl alcohol (23 mg, 0.11 mmol) and (1R) -trans-3- (2-methyl-1 -Propenyl) -2,2-dimethylcyclopropanecarboxylic acid (27 mg, 0.16 mmol) in chloroform solution (2 mL), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (31 mg, 0.16 mmol) And 4-dimethylaminopyridine (2 mg) was added. After stirring at room temperature for 20 hours, water was poured into the reaction solution, which was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and then concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain the following formula [Chemical Formula 59] (LI).
• Production Example 39 Production of Compound 291 of the Present Invention 3,5-Difluoro-2,6-dimethyl-4-methoxymethylbenzyl alcohol (106 mg, 0.49 mmol) and (1R) -trans-3- (1-propenyl)-
• To a solution of 2,2-dimethylcyclopropanecarboxylic acid (isomer ratio with respect to double bond: Z / E about 8/1) (91 mg, 0.59 mmol) in chloroform (4 mL) was added 1-ethyl-3- (3 -Dimethylaminopropyl) carbodiimide hydrochloride (113 mg, 0.59 mmol) and 4-dimethylaminopyridine (5 mg) were added.
• a part shows a mass part.
• Formulation Example 2 Compounds of the present invention 3, 9, 16, 18, 20, 22, 23, 49, 55, 59, 62, 64, 66, 69, 94, 100, 107, 109, 111, 113, 114, 186, 192, 199 , 232, 238, 245, 252, 278, 284, 291 and 298, each of 0.1 part and 39.9 parts of deodorized kerosene mixed and dissolved in an aerosol container, and after attaching the valve part, Through the part, 60 parts of propellant (liquefied petroleum gas) is pressurized and filled to obtain an oily aerosol.
• propellant liquefied petroleum gas
• Formulation Example 3 Compounds of the present invention 3, 9, 16, 18, 20, 22, 23, 49, 55, 59, 62, 64, 66, 69, 94, 100, 107, 109, 111, 113, 114, 186, 192, 199 , 232, 238, 245, 252, 278, 284, 291 and 298, respectively, 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of Rhedol MO-60 (Emulsifier, registered trademark of Kao Corporation)
• An aerosol container is filled with 50 parts of water mixed and dissolved, and 40 parts of a propellant (liquefied petroleum gas) is pressurized and filled through a valve portion to obtain an aqueous aerosol.
• a propellant liquefied petroleum gas
• Formulation Example 4 Compounds of the present invention 3, 9, 16, 18, 20, 22, 23, 49, 55, 59, 62, 64, 66, 69, 94, 100, 107, 109, 111, 113, 114, 186, 192, 199 , 232, 238, 245, 252, 278, 284, 291 and 298, respectively, and 0.5 g of BHT were mixed with a base material for mosquito coils (mixed with chrysanthemum chrysanthemum extract, wood flour, tab flour, and starch) 1) After stirring and mixing uniformly to 99.2 g, 100 mL of water containing malachite green is added as a colorant, and the kneaded mixture is molded and dried to obtain a mosquito coil.
• a base material for mosquito coils mixture of containing malachite green
• Formulation Example 6 Compounds of the present invention 3, 9, 16, 18, 20, 22, 23, 49, 55, 59, 62, 64, 66, 69, 94, 100, 107, 109, 111, 113, 114, 186, 192, 199 , 232, 238, 245, 252, 278, 284, 291 and 298 and 0.3 part of BHT are dissolved in 50 parts of a surfactant (diethylene glycol monobutyl ether) and 49 parts of purified water.
• the liquid agent is put in a polyester container, and an aqueous mosquito repellent liquid agent used in a heat transpiration device is obtained by inserting a liquid absorbent core (calculated inorganic powder) whose upper part can be heated with a heater.
• Formulation Example 7 Compounds of the present invention 3, 9, 16, 18, 20, 22, 23, 49, 55, 59, 62, 64, 66, 69, 94, 100, 107, 109, 111, 113, 114, 186, 192, 199 , 232, 238, 245, 252, 278, 284, 291 and 298, 3.0 parts of methoxadiazone and 94.0 parts of azodicarbonamide were mixed well, and 20 g of the mixture was filled in a plastic film bag. This was stored in a heat-resistant container, and an igniter was loaded to obtain a smoke agent.
• Formulation Example 8 Compounds of the present invention 3, 9, 16, 18, 20, 22, 23, 49, 55, 59, 62, 64, 66, 69, 94, 100, 107, 109, 111, 113, 114, 186, 192, 199 , 232, 238, 245, 252, 278, 284, 291 and 298 are each dissolved in an appropriate amount of acetone, uniformly applied to a non-woven fabric having a size of 5 cm ⁇ 5 cm and a thickness of 0.3 mm, and then air-dried with acetone. Get a room temperature volatilizer.
• Formulation Example 9 Compounds of the present invention 3, 9, 16, 18, 20, 22, 23, 49, 55, 59, 62, 64, 66, 69, 94, 100, 107, 109, 111, 113, 114, 186, 192, 199 , 232, 238, 245, 252, 278, 284, 291 and 298, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt, and 55 parts of water are mixed together by a wet grinding method. By pulverizing, a 10% flowable agent is obtained.
• Effect test example 1 contact test using squid 0.2% containing 0.1 mg of the compounds 94, 100, 107, 109, 111, 113, 114, 278, 284, 291 and 298 of the present invention in a petri dish having a diameter of 28 mm, an inner height of 13 mm and a bottom area of 6.15 cm 2
• Acetone solution (0.05 mL) is added dropwise and spread uniformly on the bottom, and then acetone is removed with a double ball.
• Effect test example 2 contact test using squid
• acetone is removed with a double ball.
• Effectiveness test example 3 contact test using squid
• acetone is removed with a double ball.
• Effect test example 4 room temperature volatility test using squid squid
• Ten female squids are placed in a petri dish having a diameter of 9 cm, an inner height of 1.9 cm, and a bottom area of 63.6 cm 2 and covered with a 16-mesh wire mesh.
• Compounds of the present invention 9,16,55,62,100,107,114,192,238,245,291 of drugs prepared in petri dishes of the same size (diameter 9 cm, inner height 1.9 cm, bottom area 63.6 cm 2 )
• 0.5 mL of a 2% acetone solution containing 0.09 mg of 298 was added dropwise, and the acetone was air-dried.
• the petri dish coated with this drug was placed on the wire mesh.
• Effect test example 5 (insecticidal test with mosquito coils) About 50 adult mosquitoes were released in a 70 cm cubic glass chamber, and a battery-type small fan (feather diameter 13 cm) was placed in a box and rotated. The compound 3, 9, 16, 20, 49, 55, 59, 62, 94, 100, 107, 111, 186, 192, 199, 232, 238, 245, 278, obtained by Preparation Example 4 If igniting both ends of 0.1g of 284 and 291 mosquito coils, you can knock down more than 80% of the squid within 15 minutes, and the next day can kill more than 80% of them. It was.
• Effect test example 6 (insecticidal test with smoke smoke agent)
• the compounds of the present compounds 3, 9, 16, 49, 55, 59, 62, 94, 100, 107, 111, 186, 192, 232, 238, 245, 278, 284 and 291 prepared according to Formulation Example 7
• a bag of smoke agent was heated to about 250 ° C in a 6 tatami room using a heater, the components diffused from the smoke hole formed in the plastic film throughout the room, including cockroaches, fleas and bed bugs, as well as leopard mites and mushroom mites. It was also effective in controlling indoor dust mites such as
• Effectiveness test example 7 (insecticidal test with aerosol) About 30 housefly females were released in a 60 cm cubic glass chamber, and the compound 3,9,16,49,55,59,62,94,100 of the present invention obtained by Formulation Example 2 from the hole in the side wall of the chamber. 107, 111, 113, 114, 186, 192, 199, 232, 238, 245, 252, 278, 284, 291 and 298 aerosols were sprayed for 1 second. As a result, it was confirmed that the compound of the present invention, which could knock down 100% of the house fly within 2 minutes, had a high knockdown effect.
• a part shows a mass part.
• Formulation Example 1 0.1 parts of each of the compounds 3, 9, 16 and 23 of the present invention are dissolved in 10 parts of xylene and mixed with 89.9 parts of deodorized kerosene to obtain an oil agent.
• Formulation Example 2 A solution obtained by mixing and dissolving 0.1 part of each of the compounds 3, 9, 16 and 23 of the present invention and 39.9 parts of deodorized kerosene was filled into an aerosol container, and after attaching the valve part, a propellant (liquefied) was passed through the valve part. 60 parts of petroleum gas) is pressurized and filled to obtain an oily aerosol.
• Formulation Example 3 0.6 parts of each of the compounds 3, 9, 16 and 23 of the present invention, 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of Rhedol MO-60 (emulsifier, registered trademark of Kao Corporation) An aerosol container is filled with 50 parts of water, and 40 parts of propellant (liquefied petroleum gas) is pressurized and filled through a valve part to obtain an aqueous aerosol.
• propellant liquefied petroleum gas
• Formulation Example 4 0.3 g of each of the compounds 3, 9, 16 and 23 of the present invention and 0.5 g of BHT are added to 99.2 g of a base for mosquito coils (mixed with pesticide chrysanthemum extract powder, wood powder, tab powder, and starch). After stirring and mixing uniformly, 100 mL of water containing malachite green is added as a colorant, and the mixture is sufficiently kneaded and dried to obtain a mosquito coil.
• a base for mosquito coils mixed with pesticide chrysanthemum extract powder, wood powder, tab powder, and starch.
• Formulation Example 5 Deodorized kerosene is added to and dissolved in 0.8 g of each of the compounds 3, 9, 16 and 23 of the present invention, 0.4 g of piperonyl butoxide, and the dye to make a total of 10 mL. This solution is uniformly impregnated with 0.5 mL of this solution on a mosquito mat substrate (22 mm x 35 mm, 2.8 mm thick) (a mixture of cotton linter and pulp mixed in a plate), Get.
• Formulation Example 6 A solution obtained by dissolving 0.7 parts of each of the compounds 3, 9, 16 and 23 of the present invention and 0.3 part of BHT in 50 parts of a surfactant (diethylene glycol monobutyl ether) and 49 parts of purified water is added to a polyester container.
• An aqueous mosquito repellent liquid agent used in a heat transpiration device is obtained by inserting a liquid absorption core (in which inorganic powder is baked) whose upper part can be heated with a heater.
• Formulation Example 7 After thoroughly mixing 3.0 parts of each of the compounds 3, 9, 16 and 23 of the present invention, 3.0 parts of methoxadiazone and 94.0 parts of azodicarbonamide, 20 g thereof was filled into a plastic film bag, and this was put into a heat-resistant container. A smoke agent was obtained by storing and igniter loaded.
• Formulation Example 8 10 mg of each of the compounds 3, 9, 16 and 23 of the present invention is dissolved in an appropriate amount of acetone and uniformly applied to a non-woven fabric having a size of 5 cm ⁇ 5 cm and a thickness of 0.3 mm, and then acetone is air-dried to obtain a room temperature volatilizer. .
• Formulation Example 9 By mixing 10 parts of each of the compounds 3, 9, 16 and 23 of the present invention, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt, and 55 parts of water, and finely pulverizing by a wet pulverization method, 10% flowable is obtained.
• Effect test example 1 contact test using squid
• a petri dish having a diameter of 28 mm, an inner height of 13 mm, and a bottom area of 6.15 cm 2 0.05 mL of a 0.2% acetone solution containing 0.1 mg of the compounds 3, 9, 16 and 23 of the present invention is dropped, and the bottom surface becomes uniform. After expansion, acetone is removed with a double ball.
• Effect test example 2 (insecticidal test with mosquito coils) About 50 adult mosquitoes were released in a 70 cm cubic glass chamber, and a battery-type small fan (feather diameter 13 cm) was placed in a box and rotated. When ignited at both ends of 0.1 g of the mosquito coils of the compounds 3, 9, 16 and 23 of the present invention obtained in Formulation Example 4, knock down 80% or more squid in 15 minutes The following day, more than 80% of them were killed.
• Effect test example 3 (insecticidal test with smoke smoke agent)
• one bag of smoke agent of the compounds 3, 9, 16 and 23 of the present invention prepared according to Formulation Example 7 was heated to about 250 ° C. using a heater in a 6 tatami room, a fumes hole formed of a plastic film
• the ingredients diffused throughout the room and were effective in controlling indoor dust mites such as cockroaches, fleas and bed bugs, as well as leopard mites and red mites.
• Effect test example 4 insecticidal test with aerosol
• the compound of the present invention which could knock down 100% of the house fly within 2 minutes, had a high knockdown effect.
• the compound of the present invention Since the compound of the present invention has an excellent pesticidal activity, it can be used as an active ingredient of a pesticidal agent. Further, the compound of the present invention may be used as an active ingredient of a control agent for pests that have acquired resistance, and is extremely effective.

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