JP2017214310A - Ester compound and usage thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel compound having excellent pest control effectiveness.SOLUTION: An ester compound is such a compound as expressed in a formula below.SELECTED DRAWING: None

Description

The present invention relates to an ester compound, a pest control agent and a pest control method using the ester compound.

Conventionally, various compounds have been synthesized in order to control pests (see Non-Patent Document 1). Patent Document 1 discloses certain ester compounds. However, the control efficacy of these disclosed pest control ingredients is not always satisfactory.

International Publication No. 86-02238 Specification

“Continuing Drug Development Vol. 18 Development of Agricultural Chemicals III”, Yodogawa Shoten, 1993, p. 493

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.

As a result of intensive studies, the present inventors have found that an ester compound represented by the following general formula [Chemical Formula 1] has an excellent pest control effect, and has completed the present invention.

That is, the present invention relates to the following inventions.
(1) General formula [Formula 1]
[Wherein R ¹ represents a hydrogen atom or a methyl group, when R ¹ represents a methyl group, R ² also represents a methyl group, and when R ¹ represents a hydrogen atom, R ² represents the following general formula: ]
Wherein X and Y are the same or different and each represents a hydrogen atom, a methyl group, a halogen atom, a cyano group, a lower alkyl group, a lower alkoxycarbonyl group or a lower haloalkyl group. ] The ester compound shown by this.
(2) A pest control agent comprising the ester compound according to (1) as an active ingredient.
(3) A method for controlling pests, wherein the ester compound according to (1) is applied to pests or habitats of pests.

Since the compound of the present invention has an excellent pesticidal activity, it is useful as an active ingredient of a pesticidal agent.

In the compound of the present invention, when R ¹ represents a hydrogen atom, an optical isomer derived from two asymmetric carbon atoms present at the 1-position and the 3-position on the cyclopropane ring, and a 3-position of the cyclopropane ring Although there may be isomers derived from the 1 'double bond present in the substituent, the present invention includes each isomer having pesticidal activity and any ratio of isomer mixtures.

Next, the manufacturing method of this invention compound is demonstrated.
Although this invention compound will not be specifically limited if it is a method of manufacturing a normal ester compound, For example, it can manufacture by the method shown below.
(Reference production method 1)
Formula [Chemical Formula 3]
An alcohol compound represented by
Formula [Formula 4]
[Wherein R ¹ represents a hydrogen atom or a methyl group, when R ¹ represents a methyl group, R ² also represents a methyl group, and when R ¹ represents a hydrogen atom, R ² represents the following general formula: ]
Wherein X and Y are the same or different and each represents a hydrogen atom, a methyl group, a halogen atom, a cyano group, a lower alkyl group, a lower alkoxycarbonyl group or a lower haloalkyl group. 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 [Chemical Formula 4], 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.

In the reaction, the molar ratio of the alcohol compound represented by the formula [Chemical Formula 3] and the carboxylic acid compound represented by the formula [Chemical Formula 4] or a reactive derivative thereof can be set arbitrarily, but preferably equimolar Or a ratio close to that.
The condensing agent or base can be used in an arbitrary ratio from 0.25 mol to an excess amount with respect to 1 mol of the alcohol compound represented by the formula [Chemical Formula 3], preferably 0.5 mol. ~ 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 4] 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. Can be obtained. The obtained compound of the present invention can be purified by operations such as chromatography and distillation.

(Reference production method 2)
In the above Reference Production Method 1, the alcohol compound represented by the formula [Chemical Formula 3] can be produced, for example, by the following synthetic route [Chemical Formula 6].
That is, methyl 2,3,5,6-tetrafluoro-4-methylbenzoate which is a known substance is mixed with lithium aluminum hydride in an inert solvent (for example, hexane, toluene, ether, etc.) at −30 to 20 ° C. It can manufacture by making it react for -72 hours.

On the other hand, the carboxylic acid compound represented by the general formula [Chemical Formula 4] or a reactive derivative thereof is a known substance.

Examples of the compound of the present invention include the following compounds.
Compound A of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1RS) -trans, cis-3- (2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate,
Compound B of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -trans, cis-3- (2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate,
Compound C of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -trans-3- (2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate,
Compound D of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -trans, cis-3- (2,2-difluoro-1-ethenyl) -2,2-dimethylcyclopropanecarboxylate,
The present compound E; 4-methyl-3,5,6-trifluorobenzyl (1R) -trans-3- (2,2-difluoro-1-ethenyl) -2,2-dimethylcyclopropanecarboxylate;
Compound F of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1RS) -trans, cis-3- (2,2-dichloro-1-ethenyl) -2,2-dimethylcyclopropanecarboxylate,
Compound G of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1RS) -trans-3- (2,2-dichloro-1-ethenyl) -2,2-dimethylcyclopropanecarboxylate,
Compound H of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -trans, cis-3- (2,2-dichloro-1-ethenyl) -2,2-dimethylcyclopropanecarboxylate,
Compound I of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -trans-3- (2,2-dichloro-1-ethenyl) -2,2-dimethylcyclopropanecarboxylate,
Compound J of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -trans, cis-3- (2,2-dibromo-1-ethenyl) -2,2-dimethylcyclopropanecarboxylate,
Compound K of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -cis-3- (2,2-dibromo-1-ethenyl) -2,2-dimethylcyclopropanecarboxylate,
Compound L of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1RS) -trans, cis-3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2 -Dimethylcyclopropanecarboxylate,
Compound M of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1RS) -cis-3-[(Z) -2-chloro-3,3,3-trifluoro-1-propenyl)]- 2,2-dimethylcyclopropanecarboxylate,
Compound N of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -cis-3-[(Z) -2-chloro-3,3,3-trifluoro-1-propenyl)]- 2,2-dimethylcyclopropanecarboxylate,
Compound O of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -trans, cis-3- (1-propenyl) -2,2-dimethylcyclopropanecarboxylate (isomers relating to double bonds) Ratio: Z / E = about 8/1)
Compound P of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -trans-3- (1-propenyl) -2,2-dimethylcyclopropanecarboxylate (ratio of isomers with respect to double bond) : Z / E = about 8/1)
Compound Q of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -trans, cis-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethyl Cyclopropanecarboxylate,
Compound R of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropane Carboxylate,
Compound S of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -trans, cis-3-[(Z)-(2-methoxycarbonyl-1-ethenyl)]-2,2-dimethyl Cyclopropanecarboxylate,
Compound T of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -cis-3-[(Z)-(2-methoxycarbonyl-1-ethenyl)]-2,2-dimethylcyclopropane Carboxylate,
Compound U of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -trans, cis-3-[(Z)-(2-cyano-1-propenyl)]-2,2-dimethylcyclo Propanecarboxylate,
Compound V of the present invention; 4-methyl-3,5,6-trifluorobenzyl (1R) -trans-3-[(Z)-(2-cyano-1-propenyl)]-2,2-dimethylcyclopropanecarboxy rate,
Compound W of the present invention; 4-methyl-3,5,6-trifluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate,

The pest control agent of the present invention can be used alone as a compound of the present invention alone, 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.

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 form of preparation.

Examples of 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., solid substances at room temperature (2,4,6-triisopropyl-1,3,5-trioxane, naphthalene, p-dichlorobenzene, camphor, adamantane, etc.), and Wool, silk, cotton, hemp, pulp, synthetic resin (eg, 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 and ethylene-ethyl acrylate copolymer; Ethylene-vinyl carboxylic acid such as ethylene-acrylic acid copolymer Copolymers; Polypropylene resins such as polypropylene and propylene-ethylene copolymers; poly-4-methylpentene-1, polybutene-1, polybutadiene, polystyrene; acrylonitrile-styrene resins; acrylonitrile-butadiene-styrene resins, styrene-conjugates Styrene elastomers such as diene block copolymers and hydrogenated styrene-conjugated diene block copolymers; fluororesins; acrylic resins such as polymethyl methacrylate; polyamide resins such as nylon 6 and nylon 66; Polyester resins such as rate, polyethylene naphthalate, polybutylene terephthalate; polycarbonate, polyacetal, polyarylate, hydroxybenzoic acid polyester, polyetherimide, polyester carbonate, polyphenylene ether resin, polyvinyl chloride, polyvinylidene chloride, polyurethane, Felt, fiber, cloth, knitted fabric, sheet, paper, thread, foam, porous body composed of one or more of foamed polyurethane, foamed polypropylene, foamed ethylene, etc.), glass, metal, ceramic, etc. And multifilaments.

Examples of the liquid carrier include aromatic or aliphatic hydrocarbons (xylene, alkylnaphthalene, phenylxylylethane, kerosene, light oil, hexane, cyclohexane, etc.), alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl). Alcohol, ethylene glycol, etc.), ethers (diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, tetrahydrofuran, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (acetone) , Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), nitriles (acetonitrile, isobutyronitrile) ), Sulfoxides (dimethylsulfoxide, etc.), acid amides (N, N-dimethylformamide, N-methyl-pyrrolidone, etc.), alkylidene carbonates (propylene carbonate, etc.), vegetable oils (soybean oil, cottonseed oil, etc.), plant essential oils (Orange oil, hyssop oil, lemon oil, etc.) and water.

Examples of the gaseous carrier include 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.

Other 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, etc., BHT (2,6-di-tert-butyl-4-methylphenol), and BHA (2-tert-butyl-4-methoxyphenol) 3-tert-butyl-4-methoxyphenol). Furthermore, a coloring agent, a fragrance | flavor, etc. may be mix | blended suitably as needed.

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 of the self-burning smoke agent include nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethyl cellulose, wood powder and other combustion exothermic agents, alkali metal salts, alkaline earth metal salt heat 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.

Examples of the resin used for the substrate such as a resin transpiration agent include polyethylene resins such as low density polyethylene, linear low density polyethylene, and high density polyethylene; and ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer. Polymer; ethylene-methacrylic acid ester copolymer such as ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer; ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, etc. 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 resin; Styrenic elastomer such as acrylonitrile-butadiene-styrene resin, styrene-conjugated diene block copolymer, hydrogenated styrene-conjugated diene block copolymer; Fluororesin; Acrylic resin 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, polyetherimide, polyester carbonate, polyphenylene ether resin, poly Examples thereof include vinyl chloride, polyvinylidene chloride, polyurethane and the like. These substrates may be used alone or as a mixture of two or more. Phthalates necessary to (dimethyl phthalate, dioctyl phthalate, etc.), adipic acid esters, plasticizers such as stearic acid may be added. 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 a non-heated transpiration agent, an animal collar, an animal ear tag, a sheet preparation, an attracting tape, an attracting string, and a garden support.

As a bait base, for example, 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.

As an active ingredient of such insecticides and acaricides, for example,
(1) Pyrethroid compounds pyrethrins, allethrin, praretrin, furamethrin, resmethrin, tetramethrin, imiprothrin, imiprothrin transfluthrin, methfluthrin, profluthrin, phenothrin, cyphenothrin, permethrin, cypermethrin, cypermethrin, cypermethrin. hrin), beta-cyfluthrin, fenpropathrin, bifenthrin, cycloprotorin, deltamethrin, flumethrin (flumethrin), flumethrin (flumethrin) Cyhalothrin, lambda-cyhalothrin, tefluthrin, fenvalerate, fulvalinate, etofenprox, silaflufens afluofen), Mont fluoro Trinh (momfluorothrin), dimefluthrin (dimefluthrin) or the like;
(2) Organophosphorus compounds Acephate, Butathiofos, Diazinon, Dichlorvos (DDVP), Dimethoate, Fentionion (MPP), Fenitrothion (Mentiothion) malathion), pyridafenthion, propaphos, trichlorphone (DEP) and the like;
(3) Carbamate compounds Carbaryl (carbary1), carbofuran, fenobucarb, isoprocarb (MIPC), mesomyl, NAC, propoxur (PHC), etc .;
(4) Nereistoxin compounds, such as cartap and bensultap;
(5) Neonicotinoid compounds imidacloprid (imidac1oprid), nitenpyram (nitenpyram), acetamiprid (acetamipride), thiamethoxam (thiacloprid) (thiacloprid), dinotefur (din)
(6) Benzoylurea compounds Chlorfluazuron, bistrifluron, diflubenzuron, flufenoxuron, hexafluuron, fluflutriuron, fluflutriuron etc;
(7) Phenylpyrazole compound fipronil (pyproni1), pyriprole (pyriprole), pyrafluprole (pyrafluprole) and the like;
(8) Hydrazine-based compounds Chromafenozide, halofenozide, methoxyphenozide and the like;
(9) Natural insecticide machine oil, nicotine sulfate (nicotine-sulfate);
(10) Other insecticides avermectin (vermectin-B), buprofezin, chlorfenapyr, hydroprene, metoprene, toxacarbine, indoxacarb milbemycin-A), pyridalyl, pyriproxyfen, spinosad, sulfuramid, tolfenpyrad, flubendiamide bromide, flubendiamide Examples include chill (Methyl bromide), potassium oleate (Potassium oleate), and the like.

As an active ingredient of the repellent, 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.

As an active ingredient of a 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.

Examples of 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 flea, cat flea, human flea, 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, bed bugs, etc .;
Lepidopterous pests: Japanese moths such as Japanese moth, Japanese corn borer, Japanese cypresses such as Spodoptera litura, Ayayotou, Satsuma moth, Sinigas, Hamamoga, Dokuga, Konaga, Ichimon disseri, iga, Koiga, etc .;
Coleopterous insects: weevil such as longhorn beetle, longhorn beetle, weevil, weevil, weevil such as white beetle, beetle such as white beetle, red beetle, hornet beetle, etc .;
Tick: Leopard mites, such as Scarlet mite, Yake leopard mite, Scarlet mites, such as Scarlet mite, Scarlet mite, Scarlet mites, Scarlet mites, Mite, Mite Spiders such as ticks, avian mites, and spiders.

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 application method of the pest control agent of the present invention include the following methods, which can be appropriately selected depending on the form, use place, 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.
In this case, the pest control agent of the present invention formulated in an emulsion, wettable powder, flowable agent, microcapsule preparation or the like is usually diluted so that the concentration of the compound of the present invention becomes 0.1 to 10,000 ppm. .
(3) A method of volatilizing an active ingredient by means of heating or the like in a pest habitat where the pest control agent of the present invention is present.
In this case, 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. .

When the compound of the present invention is used for pest control, 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. ˜100 mg / m ² . Mosquito coils, mosquito coils, etc. are applied by volatilizing the active ingredient by heating according to the formulation form. 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. In addition, it can be applied in open spaces outside.

When 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. As a specific method of use, for the purpose of systemic control, for example, it is administered by tablet, feed mixing, suppository, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.) For purposes of non-systemic control, for example, spraying oils or aqueous solutions, pour-on or spot-on treatment, washing animals with shampoo formulations 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 kg of animal body weight.

Hereinafter, the present invention will be described in more detail with reference to production examples, formulation examples, test examples, and the like, but the present invention is not limited to these examples.

First, the manufacture example of this invention compound is shown.
Production Example 1
Lithium aluminum hydride (292 mg, 7.69 mmol) was added to a tetrahydrofuran (20 mL) solution of methyl 4-methyl-2,3,5,6-tetrafluorobenzoate (852 mg, 3.84 mmol) under ice cooling. After stirring at room temperature for 48 hours, the reaction mixture was poured into 1N aqueous hydrochloric acid and water, and 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, and the following formula [Chem. 7]
645 mg of 4-methyl-2,3,5-trifluorobenzyl alcohol represented by

White solid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.21 (s, 3H), 4.74 (m, 2H), 6.92 (m, 1H)

Production Example 2: Production of Compound C of the Present Invention 4-Methyl-2,3,5-trifluorobenzyl alcohol (104 mg, 0.59 mmol) and (1R) -trans-3- (2-methyl-1-propenyl)- To a chloroform solution (8 mL) of 2,2-dimethylcyclopropanecarboxylic acid (140 mg, 0.83 mmol) was added 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (170 mg, 0.887 mmol) and 4-dimethyl. Aminopyridine (5 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 concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography.
4-methyl-2,3,5-trifluorobenzyl (1R) -trans-3- (2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate (the present compound C) represented by the formula: 69 mg Got.

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.14 (s, 3H), 1.26 (s, 3H), 1.43 (d, 1H), 1.69 (s , 3H), 1.71 (s, 3H), 2.08 (m, 1H), 2.22 (m, 3H) 4.89 (m, 1H), 5.30 (m, 2H) 6.86 (M, 1H)

Production Example 3: Production of Compound I of the Present Invention To a toluene solution (5 mL) of 4-methyl-2,3,5-trifluorobenzyl alcohol (110 mg, 0.63 mmol) in pyridine (98 mg, 1.24 mmol), (1R) -Trans-3- (2,2-dichloro-1-ethenyl) -2,2-dimethylcyclopropanecarboxylic acid chloride (144 mg, 0.63 mmol) was added sequentially. After stirring at room temperature for 30 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, and the following formula [Chemical Formula 9]
4-methyl-2,3,5-trifluorobenzyl (1R) -trans-3- (2,2-dichloro-1-ethenyl) -2,2-dimethylcyclopropanecarboxylate represented by formula (I) ) 189 mg was obtained.

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.18 (s, 3H), 1.29 (s, 3H), 1.64 (d, 1H), 2.22 (m , 3H), 2.26 (m, 1H), 5.15 (s, 2H), 5.61 (d, 1H), 6.86 (m, 1H)

Production Example 4: Production of Compound P of the Present Invention 4-Methyl-2,3,5-trifluorobenzyl alcohol (125 mg, 0.71 mmol) and (1R) -trans-3- (1-propenyl) -2,2- 1-Ethyl-3- (3-dimethylaminopropyl) was added to a chloroform solution (8 mL) of dimethylcyclopropanecarboxylic acid (ratio of isomers with respect to double bonds: Z / E = about 8/1) (154 mg, 0.99 mmol). ) Carbodiimide hydrochloride (205 mg, 1.07 mmol) and 4-dimethylaminopyridine (5 mg) were added. After stirring at room temperature for 24 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, and the following formula [Chemical Formula 10]
4-methyl-2,3,5-trifluorobenzyl (1R) -trans-3- (1-propenyl) -2,2-dimethylcyclopropanecarboxylate (the present compound P) represented by The ratio of isomers: Z / E = about 8/1) 57 mg was obtained.

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.16 (s, 3H, Z + E form), 1.28 (s, 3H, Z + E form), 1.50 (d, 1H, Z + E), 1.71 (dd, 3H, Z + E), 2.18 (m, 1H, Z + E), 2.21 (m, 3H, Z + E), 5.11 (m, 1H, Z + E) ), 5.14 (m, 2H, Z + E form), 5.60 (m, 1H, Z + E form), 6.87 (m, 1H, Z + E form)

Production Example 5 Production of Compound R of the Present Invention 4-Methyl-2,3,5-trifluorobenzyl alcohol (50 mg, 0.28 mmol) and (1R) -trans-3-[(E)-(2-methoxycarbonyl) -1-propenyl)]-2,2-dimethylcyclopropanecarboxylic acid (50 mg, 0.24 mmol) in chloroform solution (2 mL), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (54 mg, 0 .28 mmol) and 4-dimethylaminopyridine (2 mg) were added. After stirring at room temperature for 17 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, and the following formula [Chem. 11]
4-methyl-2,3,5-trifluorobenzyl (1R) -trans-3-[(E)-(2-methoxycarbonyl-1-propenyl)]-2,2-dimethylcyclopropanecarboxylate 59 mg of the present compound R was obtained.

Colorless liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.23 (s, 3H), 1.31 (s, 3H), 1.76 (d, 1H), 1.93 (s , 3H), 2.22 (m, 1H), 2.22 (m, 3H), 3.72 (s, 3H), 5.14 (m, 2H), 6.44 (m, 1H), 6 .85 (m, 1H)

Production Example 6 Production of Compound T of the Present Invention 4-Methyl-2,3,5-trifluorobenzyl alcohol (48 mg, 0.27 mmol) and (1R) -cis-3-[(Z)-(2-methoxycarbonyl) -1-ethenyl)]-2,2-dimethylcyclopropanecarboxylic acid (65 mg, 0.33 mmol) in chloroform (2 mL) was added 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (63 mg, 0 .33 mmol) and 4-dimethylaminopyridine (2 mg) were 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, and the following formula [Chem. 12]
4-methyl-2,3,5-trifluorobenzyl (1R) -cis-3-[(Z)-(2-methoxycarbonyl-1-ethenyl)]-2,2-dimethylcyclopropanecarboxylate 55 mg of the present compound T was obtained.

Colorless liquid: MS (EI) m / z [M] ⁺ : 356

Production Example 7 Production of Compound W of the Present Invention 4-Methyl-2,3,5-trifluorobenzyl alcohol (47 mg, 0.27 mmol) and 2,2,3,3-tetramethylcyclopropanecarboxylic acid (45 mg, 0 .32 mmol) in chloroform (2 mL) was added 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (73 mg, 0.38 mmol) and 4-dimethylaminopyridine (3 mg). After stirring at room temperature for 18 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, and the following formula [Chem. 13]
As a result, 52 mg of 4-methyl-2,3,5-trifluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate (the present compound W) was obtained.

Colorless liquid: MS (EI) m / z [M] ⁺ : 300

Next, formulation examples are shown. In addition, a part shows a mass part.

Formulation Example 1
0.1 parts of each of the compounds C, I, P, R, T and W 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 C, I, P, R, T and W of the present invention and 39.9 parts of deodorized kerosene was filled in an aerosol container, and after attaching the valve part, 60 parts of propellant (liquefied petroleum gas) is pressure-filled to obtain an oily aerosol.

Formulation Example 3
0.6 parts of each of the compounds C, I, P, R, T and W 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) are mixed and dissolved. Then, 50 parts of water is filled in an aerosol container, and 40 parts of a propellant (liquefied petroleum gas) is pressurized and filled through a valve portion to obtain an aqueous aerosol.

Formulation Example 4
Each of the compounds C, I, P, R, T and W of the present invention, 0.3 g and BHT 0.5 g, a base for mosquito coils (mixed with insecticide chrysanthemum extract powder, wood powder, tab powder, and starch) After uniformly stirring and mixing to 99.2 g, 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.

Formulation Example 5
The present compounds C, I, P, R, T and W are each 0.8 g, piperonyl butoxide 0.4 g, and the dye is added with deodorized kerosene and dissolved to make a total of 10 mL. 0.5 ml of this solution is impregnated uniformly into a substrate for mosquito mats with a thickness of 22 mm x 35 mm and a thickness of 2.8 mm (a mixture of cotton linter and pulp mixed in a plate shape) Get.

Formulation Example 6
A solution obtained by dissolving 0.7 parts of each of the compounds C, I, P, R, T and W 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. An aqueous mosquito repellent liquid agent used in a heat transpiration device is obtained by inserting a liquid absorbent core (in which inorganic powder is baked) that can be heated with a heater in a polyester container.

Formulation Example 7
100 mg of each of the compounds C, I, P, R, T and W of the present invention are dissolved in an appropriate amount of acetone and impregnated into a 4 cm × 4 cm, 1.2 cm thick porous ceramic plate to obtain a heated smoke agent.

Formulation Example 8
10 mg of each of the compounds C, I, P, R, T and W of the present invention are 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. A volatilizer is obtained.

Formulation Example 9
10 parts of each of the compounds C, I, P, R, T and W of the present invention, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt, and 55 parts of water are mixed and finely pulverized by a wet pulverization method. By doing so, a 10% flowable agent is obtained.

Next, it shows as a test example that this invention compound is effective as an active ingredient of a pest control agent.

Effect test example 1 (contact test using squid)
To 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 C, I, P and R of the present invention is dropped, and the bottom becomes uniform. After expansion, acetone is removed with a double ball. Place 3 female squids in a petri dish with each sample held on the bottom, cover the top with a perforated film, record the number of knockdowns every minute, KT ₅₀ (time to knock down 50%) The mortality after 24 hours was measured and recorded. For samples showing a predetermined value or more with respect to the knockdown rate, acetone is further added to the 0.2% acetone solution to dilute it 10-fold to obtain a 0.02% acetone solution. The method was repeated sequentially.
As a comparative control, phthalthrin: 1,3,4,5,6,7-hexahydro-1,3-dioxo-2H-isoindol-2-yl (1R) -trans, cis-3- (2-methyl- The same test was conducted using 1-propenyl) -2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as Comparative Compound A).
The results are shown in Table 1.

As a result of the test, it was found that all of the compounds C, I, P and R of the present invention showed a higher knockdown activity than the comparative compound A (phthalthrin).

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 present invention C, I, P, R and T obtained in Formulation Example 4 is knocked down 80% or more of the squid in 15 minutes. More than 80% of them were killed the next day.

Effect test example 3 (insecticidal test with smoke smoke agent)
When one bag of the present compound C, I, P, R and T of the present invention prepared according to Formulation Example 7 was heated to about 250 ° C. using a heater in a 6 tatami room, it was formed of a plastic film. The components diffused from the fumarole, and were effective in controlling indoor dust mites such as cockroaches, fleas, bed bugs, leopard mites, and white mites.

Effect test example 4 (insecticidal test with aerosol)
Approximately 30 adult houseflies are released in a 60 cm cubic glass chamber, and aerosols of the compounds C, I, P, R, T and W of the present invention obtained in Formulation Example 2 are sprayed for 1 second from the hole in the side wall of the chamber. did. 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.

Since the compound of the present invention has an excellent pesticidal activity, it is useful as an active ingredient of a pesticidal agent.

Claims (3)

[Formula 1]
[Wherein R ¹ represents a hydrogen atom or a methyl group, when R ¹ represents a methyl group, R ² also represents a methyl group, and when R ¹ represents a hydrogen atom, R ² represents the following general formula: ]
Wherein X and Y are the same or different and each represents a hydrogen atom, a methyl group, a halogen atom, a cyano group, a lower alkyl group, a lower alkoxycarbonyl group or a lower haloalkyl group. ] The ester compound shown by this. A pest control agent comprising the ester compound according to claim 1 as an active ingredient. A method for controlling pests, wherein the ester compound according to claim 1 is applied to pests or habitats of pests.