WO2009064025A1 - Cyclopropanecarboxylate and use thereof - Google Patents

Abstract

There is provided a novel cyclopropanecarboxyate of the formula (1): wherein R1 represents a hydrogen atom, a fluorine atom, a C1-C4 alkyl group, a C2-C4 alkenyl group, a C2-C4 alkynyl group, a C1-C4 alkoxy group, a (C1-C4 alkyl)oxymethyl group or a (C1-C4 alkyl)thiomethyl group. The cyclopropanecarboxyate has excellent pest control effect.

Description

DESCRIPTION

CYCLOPROPANECARBOXYLATE AND USE THEREOF

Technical Field

The present invention relates to a cyclopropanecarboxylate and the use thereof.

Background Art Heretofore, a number of compounds have been synthesized for controlling pests. For example, a certain kind of cyclopropanecarboxylate derivatives is described in JP 53-108951 A. However, the pest controlling effect of the cyclopropanecarboxylate derivative described in the above document is not high enough.

Disclosure of the Invention

An object of the present invention is to provide a novel compound having an excellent pest controlling effect. The present inventors have intensively studied and have found that an ester compound of the formula (1) shown hereinafter has an excellent pest controlling effect. Thus, the present invention has been completed.

That is, the present invention provides: [1] A cyclopropanecarboxylate of the formula (1) :

[wherein R¹ represents a hydrogen atom, a fluorine atom, a

C1-C4 alkyl group, a C2-C4 alkenyl group, a C2-C4 alkynyl group, a C1-C4 alkoxy group, a (C1-C4 alkyl) oxymethyl group or a (C1-C4 alkyl) thiomethyl group (hereinafter, sometimes, referred to as the present compound) ;

[2] The cyclopropanecarboxylate according to [1], wherein R¹ is a hydrogen atom, a fluorine atom, a methyl group, a 2-propenyl group, a 2-propynyl group, a methoxy group, a methoxymethyl group or a methylthiomethyl group; [3] A pest controlling composition, which comprises the cyclopropanecarboxylate according to [1] or [2] as an active ingredient;

[4] A pest controlling method, which comprises applying an effective amount of the cyclopropanecarboxylate according to [1] or [2] to a pest or a habitat of the pest; and

[5] A process for producing the cyclopropanecarboxylate according to [1] or [2], which comprises the steps of reacting a compound of the formula (6) :

with a periodate in the presence of an oxide of manganese or ruthenium to obtain a carboxylic acid of the formula (3) :

and reacting the carboxylic acid of the formula (3) with an alcohol of the formula (2) :

wherein R¹ represents a hydrogen atom, a fluorine atom, a

C1-C4 alkyl group, a C2-C4 alkenyl group, a C2-C4 alkynyl group, a C1-C4 alkoxy group, a (C1-C4 alkyl) oxymethyl group or a (C1-C4 alkyl) thiomethyl group] to obtain the cyclopropanecarboxylate .

Since the present compound has an excellent pest controlling effect, it is useful as an active ingredient of a pest controlling composition.

Best Mode for Carrying Out the Invention

In the present compound, there exist two asymmetric carbons at the 1- and 3-positions on the cyclopropane ring.

The absolute configuration of the Ci carbon atom of the cyclopropane ring is R-configuration and that of the C3 carbon atom is S. The relative stereochemistry of Cl and C3 carbon atoms is cis. That is, the present compound is a

( IR) -cis-cyclopropanecarboxylate . In the present invention, examples of the C1-C4 alkyl group include a methyl group, an ethyl group and a propyl group; examples of the C2-C4 alkenyl group include a vinyl group and a 2-propenyl group; examples of the C2-C4 alkynyl group include an ethynyl group and a 2-propynyl group; examples of the C1-C4 alkoxy group include a methoxy group, an ethoxy group and a propoxy group; examples of the (C1-C4 alkyl) oxymethyl group include a methoxymethyl group, an ethoxymethyl group and a propoxymethyl group; and examples of the (C1-C4 alkyl) thiomethyl group include a methylthiomethyl group, an ethylthiomethyl group and a propylthiomethyl group.

The present compound can be produced, for example, by using an alcohol of the formula (2) :

wherein R¹ is as described above, and a carboxylic acid of the formula (3) :

or a reactive derivative thereof as the starting materials.

This reaction is usually carried out in a solvent in the presence of a base. Examples of the base for this reaction include organic bases such as triethylamine, pyridine, N, N-diethylaniline, 4-dimethylaminopyridine and diisopropylethylamine . The solvent for this reaction includes those inert in the reaction. Specific examples thereof include hydrocarbons such as toluene and hexane; ethers such as diethyl ether and tetrahydrofuran; halogenated hydrocarbons such as chloroform, dichloromethane and 1, 2-dichloroethane; and a mixed solvent thereof. Examples of the reactive derivative include an acid halide of the carboxylic acid, an acid anhydride of the carboxylic acid and a lower alkyl ester of the carboxylic acid.

The reaction time of this reaction is usually from an instant to 72 hours, and the reaction temperature is usually in a range from -2O⁰C to 100°C.

The alcohol compound is used theoretically in an amount of 1 mol per mol of the carboxylic acid or its reactive derivative for the reaction, appropriately in an amount of 0.5 to 1.5 mol per it. The amount of the base for this reaction is usually 1 mol per mol of the carboxylic acid or its reactive derivative, but it can appropriately be selected according to the reaction conditions .

After completion of this reaction, the present compound can be isolated, for example, by subjecting the reaction mixture to conventional workup such as pouring into water, followed by extraction with an organic solvent and further concentration. If necessary, the present compound thus isolated can be purified by chromatography and distillation.

The alcohol compound of the formula (2) is described in JP 56-97251 A, JP 57-123146 A, JP 61-207361 A and JP 11- 222463, and can be produced according to the processes described in these documents.

The carboxylic acid of the formula (3) can be produced, for example, by a process of the step 1 described hereinafter. The reactive derivative of the carboxylic acid can be prepared by a known process, using the carboxylic acid of the formula (3) as a starting material.

Preferably, the present compound can be simply produced by a process comprising the steps of reacting a compound of the formula (6) :

with a periodate in the presence of an oxide of manganese or ruthenium to obtain the carboxylic acid of the formula (3) (hereinafter referred to as the step 1); and then reacting the resultant carboxylic acid of the formula (3) with an alcohol of the formula (2) to obtain the present compound (hereinafter referred to as the step 2) . The reaction of the step 1 is usually carried out in the presence of a solvent. The solvent for this reaction includes water as well as a mixed solvent of water and an organic solvent miscible with water. Examples of the organic solvent miscible with water include alcoholic solvents such as tert-butyl alcohol; ketone solvents such as acetone and methyl ethyl ketone; nitrile solvents such as acetonitrile and propionitrile; and amide solvents such as N, N-dimethylformamide and N-methyl pyrrolidone.

Examples of the periodate include sodium metaperiodate and potassium metaperiodate .

Examples of the oxide of manganese include sodium permanganate and potassium permanganate. Examples of the oxide of ruthenium include anhydrous ruthenium (IV) oxide and ruthenium (IV) oxide hydrate. It is possible that the oxide of manganese or ruthenium can be prepared in the same reaction medium before the step 1.

The amount of the oxide of manganese or ruthenium for this reaction is usually from 0.1 to 1 mol per mol of the compound of the formula (6) , and the amount of the periodate is usually from 2 to 30 mol per mol of the compound of the formula (6) .

The reaction time of this reaction is usually between 12 and 96 hours, and the reaction temperature is usually from 0 to 50⁰C.

After completion of the reaction, the compound of the formula (3) can be isolated, for example, by subjecting the reaction mixture to conventional workup such as pouring into water, followed by extraction with an organic solvent and further concentration.

The reaction of the step 2 is usually carried out in a solvent in the presence of an acid catalyst or a condensing agent. The solvent for this reaction includes those inert in the reaction. Specific examples thereof include hydrocarbons such as toluene and hexane; ethers such as diethyl ether and tetrahydrofuran; halogenated hydrocarbons such as chloroform, dichloromethane and 1, 2-dichloroethane; and a mixed solvent thereof.

Examples of the acid catalyst include inorganic acids such as sulfuric acid; and sulfonic acids such as paratoluenesulfonic acid and methanesulfonic acid. The amount of the acid catalyst for this reaction is usually in a range from 0.01 to 20 mol per mol of the carboxylic acid, but it can appropriately be selected according to the reaction conditions.

Examples of the condensing agent in this reaction include dicyclohexylcarbodiimide and l-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride. The amount of the condensing agent for this reaction is usually 1 mol per mol of the carboxylic acid, but it can appropriately be selected according to the reaction conditions.

In the step 2, the reaction time is usually between an instant to 72 hours, and the reaction temperature is in a range from -20°C to 100⁰C. After completion of the reaction, the present compound can be isolated, for example, by subjecting the reaction mixture to conventional workup such as pouring into water, followed by extraction with an organic solvent and further concentration. If necessary, the present compound thus isolated is purified by chromatography and distillation. The compound of the formula (6) is, for example, prepared according to the process described in JP 5-246971 A or J. Org. Chem. 2003, 68, 621-624, or by a process shown in the following scheme.

The reaction from the compound of the formula (4) to the compound of the formula (5)

This reaction is carried out by reacting the compound of the formula (4) with a chlorinating agent (e.g., oxalyl chloride), followed by reaction with ammonia.

This reaction is usually carried out in a solvent. Examples of the solvent for this reaction include ether solvents such as tetrahydrofuran .

The amount of the chlorinating agent for this reaction is theoretically 1 mol per mol of the compound of the formula (4), but can appropriately be selected in a range from 1 mol to an excess amount, and preferably from 1 mol to 3 mol. The compound of the formula (4) can react with the chlorinating agent, if necessary, in the presence of a base. Examples of the base include triethylamine and pyridine. The reaction of the compound of the formula (4) with the chlorinating agent is carried out usually for 1 to 24 hours. The reaction temperature is usually from 0°C to 50°C.

The reaction with ammonia is usually carried out by injecting ammonia gas or aqueous ammonia into the reaction mixture of the above step or its concentrate.

The amount of ammonia is theoretically 1 mol per mol of the compound of the formula (4), but can appropriately be selected in a range from 1 mol to a large excess amount, and preferably from 1 mol to 3 mol. The reaction time for carrying out the reaction with ammonia is usually from 1 to 24 hours, and the reaction temperature is usually from 0°C to 50°C.

After completion of the reaction, the compound of the formula (5) can be isolated, for example, by subjecting the reaction mixture to conventional workup such as pouring into water, followed by extraction with an organic solvent and further concentration.

The reaction from the compound of the formula (5) to the compound represent by the formula (6)

This reaction is carried out by reacting the compound of the formula (5) with acetic anhydride.

The amount of the acetic anhydride in this reaction is in a range from 5 mol to a large excess amount per 1 mol of the compound of the formula (5) . The reaction time of this reaction is usually in a range from 1 to 24 hours, and the reaction temperature is usually in a range from 25°C to a reflux temperature of acetic anhydride. After completion of the reaction, the compound of the formula (6) can be isolated, for example, by subjecting the reaction mixture to conventional workup such as pouring into water, followed by extraction with an organic solvent and further concentration. If necessary, the isolated compound of the formula (6) thus obtained is purified by chromatography .

The compound of the formula (4) can be prepared, for example, by appropriately purifying chrysanthemic acid prepared according to the process described in JP 2001- 278851 A, or obtained from a filtrate prepared by a purification method according to an optical resolution described in JP 11-279111 A.

Examples of the pests on which the present compound exerts an effect include harmful arthropods such as harmful insects and ticks. Specific examples thereof are as follows .

Lepidoptera :

Pyralidae such as Chilo suppressalis, Cnaphalocrocis medinalis and Plodia interpunctella, Noctuidae such as Spodoptera litura, Pseudaletia separate and Mamestra brassicae, Pieridae such as Pieris rapae crucivora, Tortricidae such as Adoxophyes spp., Carposinidae, Lyonetiidae, Lymantriidae, Antographa, Agrothis spp. such as Agrotis segetum and Agrotis ipsilon, Helicoverpa spp., Heliothis spp., Plutella xylostella, Parnara guttata, Tinea translucens, Tineola bisselliella, etc.

Diptera :

Culex spp. such as Culex pipiens pallens and Culex tritaeniorhynchus, Aedes spp. such as Aedes aegypti and Aedes albopictus, Anopheles spp. such as Anopheles sinensis, Chironomidae, Muscidae such as Musca domestica, Muscina stabulans and Fannia canicularis, Calliphoridae, Sarcophagidae, Anthomyiidae such as Delia platura and Delia antiqua, Tephritidae, Agromyzidae, Drosophilidae, Psychodidae, Phoridae, Tabanidae, Simuliidae, Stomoxyidae, Ceratopogonidae, etc.

Blattaria :

Blattella germanica, Periplaneta fuliginosa, Periplaneta americana, Periplaneta brunnea, Blatta orientalis, etc.

Hymenoptera :

Formicidae, Vespidae, Bethylidae, Tenthredinidae such as Athalia rosae ruficornis, etc.

Siphonaptera : Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, etc.

Anoplura :

Pediculus humanus, Pthirus pubis, Pediculus capitis, Pediculus corporis, etc. Isoptera:

Reticulitermes speratus, Coptotermes formosanus, etc.

Hemiptera :

Delphacidae such as Laodelphax striatellus,

Nilaparvata lugens and Sogatella furcifera, Deltocephalidae such as Nephotettix virescens and Nephotettix cincticeps, Aphididae, Pentatomidae, Aleyrodidae, Coccoidea, Cimicidae such as Cimex lectularius, Tingidae, Psyllidae, etc.

Coleoptera :

Attagenus unicolor japonicus, Authrenus verbasci, Corn Rootwarms such as Diabrotica virgifera and Diabrotica undecimpunctata howardi, Scarabaeidae such as Anomala cuprea and Anomala rufocuprea, Curculionidae such as Sitophilus zeamais, Lissorhoptrus oryzophilus, Anthonomus grandis grandis and Callosobruchus chinensis, Tenebrionidae such as Tenebrio molitor and Tribolium castaneum,

Chrysomelidae such as Oulema oryzae, Phyllotreta striolata and Aulacophora femoralis, Anobiidae, Epilachna spp . such as Epilachna vigintioctopunctata, Lyctidae, Bostrychidae, Cerambycidae, Paederus fuscipes, etc. Thysanoptera : Thrips palmi, Flankliniella occidentalis, Thrips hawaiiensiS_f etc. Orthoptera :

Gryllotalpidae, Acrididae, etc. Acarina:

Pyroglyphidae such as Dermatophagoides farinae and Dermatophagoides pteronyssinus, Acaridae such as Tyrophagus putrescentiae and Aleuroglyphus ovatus, Glycyphagidae such as Glycyphagus privatus, Glycyphagus domesticus and Glycyphagus destructor, Cheyletidae such as Cheyletus malaccensis and Cheyletus fortis, Tarsonemidae, Chortoglyphus spp., Oribatei, Tetranychidae such as Tetranychus urticae, Tetranychus kanzawai, Panonychus citri and Panonychus ulmi, Ixodidae such as Haemaphysalis longicornis, Dermanyssidae such as Ornithonyssus sylviarum and Dermanyssus galllnae, etc.

The pest controlling composition of the present invention can be the present compound itself, but is usually formulated into the following formulation forms. Examples of the formulation include oil solution, emulsifiable concentrate, wettable powder, flowable formulation (e.g., aqueous suspension and aqueous emulsion), microcapsule, dust, granule, tablet, aerosol, carbon dioxide formulation, heat transpiration formulation (e.g., pesticidal incense, electric pesticidal mat and liquid absorbing core-type heat transpiration pesticide) , piezo pesticidal formulation, heat fumigant (e.g., self combustion-type fumigant, chemical reaction-type fumigant and porous ceramic plate fumigant), unheated transpiration formulation (e.g., resin transpiration formulation, paper transpiration formulation, unwoven fabric transpiration formulation, knit fabric transpiration formulation and sublimating tablet), aerosol formulation (e.g., fogging formulation), direct contact formulation (e.g., sheet- shaped contact formulation, tape-shaped contact formulation and net-shaped contact formulation) , ULV formulation and poison bait.

Examples of the formulation method are as follows.

(1) A method comprising mixing the present compound with a solid carrier, liquid carrier, gaseous carrier or poison bait, followed by addition of a surfactant and other auxiliary agents for formulations, and if necessary, further processing.

(2) A method comprising impregnation the present compound in a base material containing no active ingredient.

(3) A method comprising mixing the present compound and a base material, followed by subjecting the mixture to mold processing.

These formulations usually contain the present compound in an amount of 0.001 to 98% by weight, although the amount is different depending on the formulation form.

Examples of the solid carrier for the formulation method include fine powders or granules of clays (e.g., kaolin clay, diatom earth, bentonite, Fubasami clay and acid white clay) , synthetic hydrated silicon oxide, talc, ceramics, other inorganic minerals (e.g., sericite, quartz, sulfur, active carbon, calcium carbonate and hydrated silica) and chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium chloride and urea); substances that are solid at room temperature (e.g., 2, 4 , 6-triisopropyl-l, 3, 5-trioxane, naphthalene, p- dichlorobenzene, camphor and adamantine) ; as well as felt, fiber, fabric, knit, sheet, paper, thread, foam, porous material and multi-filament, which respectively comprise one or more substances selected from wool, silk, cotton, hemp, pulp, synthetic resin, glass, metal and ceramics.

Examples of the synthetic resin for the solid carrier include polyethylene resins such as low density polyethylene, straight chain low density polyethylene and high density polyethylene; ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer; ethylene- methacrylic acid ester copolymers such as ethylene- methacrylic acid methyl copolymer and ethylene-methacrylic acid ethyl copolymer; ethylene-acrylic acid ester copolymers such as ethylene-acrylic acid methyl copolymer and ethylene-acrylic acid ethyl copolymer; ethylene- vinylcarboxylic acid copolymers such as ethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymer; polypropylene resins such as propylene homopolymer and propylene-ethylene copolymer; poly-4-methylpentene-l, polybutene-1, polybutadiene, polystyrene; acrylonitrile- styrene resin; acrylonitrile-butadiene-styrene resin; styrene elastomers such as styrene-conjugated diene block copolymer and hydrogenated styrene-conjugated diene block copolymer; fluorine resin; acrylic resin such as polymethacrylic acid methyl; polyamide resins such as nylon 6 and nylon 66; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate and polycyclohexylene dimethylene terephthalate; and porous resins such as polycarbonate, polyacetal, polyacryl sulfone, polyacrylate, hydroxybenzoic acid polyester, polyetherimide, polyester carbonate, polyphenylene ether resin, polyvinyl chloride, polyvinylidene chloride, polyurethane, polyurethane foam, polypropylene foam and ethylene foam.

Examples of the liquid carrier include aromatic or aliphatic hydrocarbons (e.g., xylene, toluene, alkylnaphthalene, phenylxylylethane, kerosene, light oil, hexane and cyclohexane) , halogenated hydrocarbons (e.g., chlorobenzene, dichloromethane, dichloroethane and trichloroethane) , alcohols (e.g., methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol and ethylene glycol), ethers (e.g., diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran and dioxane) , esters (e.g., ethyl acetate and butyl acetate), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone) , nitriles (e.g., acetonitrile and isobutyronitrile) , sulfoxides (e.g., dimethyl sulfoxide), acid amides (e.g., N, N-dimethylformamide, N, N- dimethylacetamide and N-methyl-pyrrolidone) , alkylidene carbonate (e.g., propylene carbonate), vegetable oils (e.g., soybean oil and cotton oil), plant essential oils (e.g., orange oil, hyssop oil and lemon oil), and water.

Examples of the gaseous carrier include butane gas, chlorofluorocarbon, liquefied petroleum gas (LPG) , dimethyl ether and carbon dioxide.

Examples of the surfactant include alkyl sulfuric acid ester salts, alkyl sulfonate, alkylaryl sulfonate, alkylaryl ethers, polyoxyethylenated alkylaryl ethers, polyethylene glycol ethers, polyhydric alcohol esters and sugar alcohol derivatives.

Examples of the other auxiliary agents for formulations include binder, dispersant and stabilizer. Specifically, there are, for example, casein, gelatin, saccharides (e.g., starch, gum arabic, cellulose derivatives and alginic acid) , lignin derivatives, bentonite, sucrose, synthetic water-soluble polymers (e.g., polyvinyl alcohol and polyvinyl pyrrolidone) , polyacrylic acid, BHT (2, β-di-tert-butyl-4-methylphenyl) and BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4- methoxyphenol) .

Examples of the base material for pesticidal incense 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 the base material for electric pesticidal mat include cotton linter hardened in a plate form and fibrils of a mixture of cotton linter and pulp hardened in a plate form.

Examples of the base material of 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 diatom earth, and binders such as synthetic glue. Examples of the base material for 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. Examples of the base material for resin transpiration formulation include polyethylene resins such as low density polyethylene, straight chain low density polyethylene and high density polyethylene; ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer; ethylene- methacrylic acid ester copolymers such as ethylene- methacrylic acid methyl copolymer and ethylene-methacrylic acid ethyl copolymer; ethylene-acrylic acid ester copolymers such as ethylene-acrylic acid methyl copolymer and ethylene-acrylic acid ethyl copolymer; ethylene- vinylcarboxylic acid copolymers such as ethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymer; polypropylene resins such as propylene copolymer and propylene-ethylene copolymer; poly-4-methylpentene-l, polybutene-1, polybutadiene, polystyrene, acrylonitrile- styrene resin; acrylonitrile-butadiene-styrene resin; styrene elastomers such as styrene-conjugated diene block copolymer and hydrogenated styrene-conjugated diene block copolymer; fluorine resin; an acrylic resin such as polymethacrylic acid methyl; polyamide resins such as nylon 6 and nylon 66; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate and polycyclohexylene dimethylene terephthalate; polycarbonate, polyacetal, polyacryl sulfone, polyacrylate, hydroxybenzoic acid polyester, polyetherimide, polyester carbonate, polyphenylene ether resin, polyvinyl chloride, polyvinylidene chloride and polyurethane . These base materials can be used alone, or by combining two or more kinds thereof. If necessary, a plasticizer such as phthalic acid ester (e.g., dimethyl phthalate and dioctyl phthalate) , adipic acid ester and stearic acid can be added to these base materials. The resin transpiration formulation is prepared by mixing the present compound with the above 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 a plate, film, tape, net or string shape. These resin formulations are processed into animal collars, animal ear tags, sheet products, trap strings, gardening supports and other products. Examples of the base material for poison bait include food 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 controlling method of the present invention is carried out by applying an effective amount of the present compound to a pest or a habitat thereof, usually in a form of the pest controlling composition of the present invention .

The application method of the pest controlling composition of the present invention is appropriately selected according to a form of the composition and an area to be used. For example, the following methods are employed.

(1) A method comprising applying the pest controlling composition of the present invention as it is to a pest or a habitat of the pest.

(2) A method comprising diluting the pest controlling composition of the present invention with a solvent such as water, and then spraying the diluted composition to a pest or a habitat of the pest. In this method, the pest controlling composition of the present invention, which is usually formulated into an emulsifiable concentrate, a wettable powder, a flowable formulation, microcapsules or other formulations, is diluted to the concentration of the present compound being 0.1 to 10,000 ppm.

(3) A method comprising heating the pest controlling composition of the present invention at a habitat of a pest, to volatilize and diffuse the active ingredient. In this method, the amount and concentration of the present compound to be applied can appropriately be determined according to the form, application period, application area, application method, kind of a pest, damage to be incurred and other factors. The amount of the present compound for controlling epidemics is usually from 0.0001 to 1000 mg/m³ in the case applying it to space. The amount is from 0.0001 to 1,000 mg/m² in the case of applying it to a plane. The pesticidal incense or electric pesticidal mat is applied by heating it according to its form to volatilize and diffuse the active ingredient. The resin transpiration formulation, paper transpiration formulation, unwoven fabric transpiration formulation, knit fabric transpiration formulation or sublimating tablet is applied by allowing it to stand in space to be applied, or by placing it in an air flow .

Examples of the space where the pest controlling composition of the present invention is applied for controlling epidemics include closet, dresser, wardrobe, chest, cupboard, toilet, bathroom, storehouse, living room, dining room, garage and car interior. The present composition can also be applied to outdoor open space.

When the pest controlling composition of the present invention is used to livestock such as cows, horses, pigs, sheep, goats and chickens, and small animals such as dogs, cats, rats and mice, for the purpose of controlling external parasites, veterinary known methods are applied to the animals. Specifically, the formulation is administered by way of tablet, mixing in feed, suppository and injection (including intramuscular, subcutaneous, intravenous and intraperitoneal injections), when systemic control is intended. On the other hand, it is used by way of spraying the oil solution or aqueous solution, pour-on or spot-on treatment, washing an animal with a shampoo formulation, or putting a collar or ear tag made of the resin formulation to an animal, when non-systemic control is intended. The dosage of the present compound is usually in the range from 0.01 to 1000 mg per 1 kg of an animal body.

The pest controlling composition of the present invention can be used in a mixture or combination with one or more other insecticides, acaricides, nematocides, soil pest controlling agents, fungicides, herbicides, plant growth regulating substances, repellents, synergists, fertilizers, and soil conditioners. Examples of the active ingredient for the insecticide and the acaricide include organic phosphorous compounds such as dichlorvos, fenitrothion, cyanophos, profenofos, sulprofos, phenthoate, isoxathion, tetrachlorvinphos, fenthion, chlorpyrifos, diazinon, acephate, terbufos, phorate, chlorethoxyfos, fosthiazate, ethoprophos, cadusafos, methidathion, disulfoton, dioxabenzofos, dimethoate, phenthoate, malathion, trichlorphon, azinphos-methyl, monocrotophos, ethion, etc . ; carbamate compounds such as propoxur, carbaryl, metoxadiazone, fenobucarb, methomyl, thiodicarb, alanycarb, benfuracarb, oxamyl, aldicarb, methiocarb, carbosulfan, ethiofencarb, fenothiocarb, cartap, etc.; pyrethroid compounds such as allethrin, tralomethrin, prallethrin, d-phenothrin, d-resmethrin, cyphenothrin, permethrin, cypermethrin, alpha-cypermethrin, zeta- cypermethrin, deltamethrin, tralomethrin, cyfluthrin, beta- cyfluthrin, cyhalothrin, lambda-cyhalothrin, d- furamethrin, imiprothrin, ethofenprox, fenvalerate, esfenvalerate, fenpropathrin, silafluofen, bifenthrin, transfluthrin, flucythrinate, tau-fluvalinate, acrinathrin, tefluthrin, cycloprothrin, metofluthrin, profluthrin, dimefluthrin, empenthrin, flumethrin, fluvalinate, 2-methyl-2- (4- bromodifluoromethoxyphenyl) propyl (3-phenoxybenzyl) ether, and 5- (2-propynyl) furfuryl 2, 2, 3, 3-tetramethylcyclopropane carboxylate;

Neonicotinoid compounds such as acetamiprid, nitenpyram, thiacloprid, thiamethoxam, dinotefuran, clothianidine, imidacloprid, etc.; chlorinated hydrocarbon compounds such as endosulfan, γ-BHC and 1, 1-bis (chlorophenyl) -2, 2, 2-trichloroethanol; benzoylphenyl urea compounds such as lufenuron, chlorfluazuron, hexaflumuron, diflubenzuron, triflumuron, teflubenzuron, flufenoxuron, fluazuron, novaluron, triazuron, bistrifluron, flufenoxuron, etc.; juvenile hormone analogues such as pyriproxyfen, methoprene, hydroprene, phenoxycarb, etc.; phenylpyrazole compounds such as pyriprole, pyrafluprole, ethiprole, etc.; benzoylhydrazine compounds such as tebufenozide, chromafenozide, methoxyfenozide, halofenozide, etc.; macrolide compounds such as polynactin complex ( tetranactin, dinactine and trinactin) , abamectin, avermectin, emamectin benzoate, spinosad, azadirachtin, milbemectin, etc.; and diafenthiuron, pymetrozine, flonicamide, triazamate, buprofezin, spinosad, emamectin benzoate, chlorphenapyr, indoxacarb MP, pyridalyl, cyromazine, fenpyroximate, tebufenpyrad, tolefenpyrad, pyridaben, pyrimidifen, fluacrypyrim, etoxazole, fenazaquin, acequinocyl, hexythiazox, clofentezine, fenbutatin oxide, dicofol, propargite, abamectin, avermectin, milbemectin, amitraz, bensultap, thiocyclam, endosulfan, spirodiclofen, spiromesifen, amidoflumet and azadirachtin, bromopropylate, tetradifon, chinomethionat, polynactin complex (tetranactin, dinactin and trinactin) , abamectin, metaflumizon, flubendiamide, chlorantraniliprole and pyrifluquinazon.

Examples of the active ingredient of the repellent - include 3, 4-caranediol, N, N-diethyl-m-toluamide, 1- methylpropyl 2- (2-hydroxyethyl) -1-piperidine carboxylate, p-menthan-3, 8-diol and an essential oil such as a hyssop oil.

Examples of the active ingredient of the synergist include bis- (2, 3, 3, 3-tetrachloropropyl) ether (S-421), N- (2-ethylhexyl) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxyimide (MGK-264) and A- [2- (2-butoxyethoxy) ethoxy] -4 , 5- methylenedioxy-2-propyltoluene (piperonyl butoxide) .

The present invention will be described in more detail by way of Production Examples, Formulation Examples and Test Examples, but it is not limited thereto. First, Production Examples of the present compound will be described. Production Example 1

Under a nitrogen atmosphere, 182 mg of l-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride was added to a mixture of 128 mg of 2, 3, 5, 6-tetrafluorobenzyl alcohol, 128 mg of (IR) -cis-3-cyano-2, 2- dimethylcyclopropanecarboxylic acid, 5 mg of 4- dimethylaminopyridine and 5 mL of chloroform, followed by stirring the mixture at room temperature for 18 hours. The reaction mixture was added to water, followed by extraction with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. To a solution of the residue dissolved in 5 mL of anhydrous tetrahydrofuran were added 0.06 mL of triethylamine, 0.04 mL of acetic anhydride and 5 mg of 4- dimethylaminopyridine, followed by stirring the mixture at room temperature for 18 hours to acetylate the remaining benzyl alcohol. To the reaction mixture was added an aqueous saturated sodium bicarbonate solution, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The resultant residue was subjected to silica gel chromatography to obtain 34 mg of 2,3,5,6- tetrafluorobenzyl (IR) -cis-3-cyano-2, 2-dimethylcyclopropane carboxylate represented by the following formula:

(hereinafter referred to as the present compound (I)) as a colorless liquid. 1H-NMR (CDCl₃, TMS) δ (ppm) : 1.28 (s, 3H), 1.46 (s,3H), 1.77 (d, IH, J = 8.2 Hz), 1.96 (d, IH, J = 8.2 Hz ), 5.29 (d, IH, J = 12.3 Hz ), 5.34 (d, IH, J = 12.3 Hz ), 7.10-7.14 (m, IH) Production Example 2

The same procedure as that in Production Example 1 was carried out except for using 4-methyl-2 , 3, 5, 6- tetrafluorobenzyl alcohol instead of 2,3,5,6- tetrafluorobenzyl alcohol to obtain 4-methyl-2 , 3, 5, 6- tetrafluorobenzyl (IR) -cis-3-cyano-2 , 2-dimethylcyclopropane carboxylate represented by the following formula:

(hereinafter referred to as the present compound (2)) as a colorless liquid.

¹H-NMR (CDCl₃, TMS) δ (ppm) : 1.27 (s, 3H), 1.46 (s, 3H), 1.76 (d, IH, J = 8.3 Hz), 1.96 (d, IH, J = 8.3 Hz ), 2.29 (t, 3H, J = 2.1 Hz), 5.26 (d, IH, J = 12.2 Hz ), 5.31 (d, IH, J = 12.2 Hz ) Production Example 3

The same procedure as that in Production Example 1 was carried out except for using 4-methoxy-2, 3, 5, 6- tetrafluorobenzyl alcohol instead of 2,3,5,6- tetrafluorobenzyl alcohol to obtain 4-methoxy-2, 3, 5, 6- tetrafluorobenzyl (IR) -cis-3-cyano-2, 2-dimethylcyclopropane carboxylate represented by the following formula:

(hereinafter referred to as the present compound (3)) as a colorless liquid.

¹H-NMR (CDCl₃, TMS) δ (ppm) : 1.28(s, 3H), 1.46 (s, 3H), 1.76

(d, IH, J = 8.3 Hz), 1.95 (d, IH, J = 8.3 Hz ), 4.11 (t, 3H, J = 1.6 Hz), 5.21-5.30 (m, 2H ) Production Example 4

The same procedure as that in Production Example 1 was carried out except for using 4-methoxymethyl-2, 3, 5, 6- tetrafluorobenzyl alcohol instead of 2,3,5,6- tetrafluorobenzyl alcohol to obtain 4-methoxymethyl- 2,3,5, 6-tetrafluorobenzyl (IR) -cis-3-cyano-2,2- dimethylcyclopropane carboxylate represented by the following formula:

(hereinafter referred to as the present compound (4)) as a colorless liquid.

¹H-NMR (CDCl₃, TMS) δ (ppm) : 1.28 (s, 3H), 1.46 (s, 3H), 1.77 (d, IH, J = 8.5 Hz), 1.95 (d, IH, J = 8.5 Hz ), 3.41 (s, 3H), 4.59 (s, 2H), 5.28 (d, IH, J =12.1 Hz), 5.34 (d, IH, J =12.1 Hz) Production Example 5

The same procedure as that in Production Example 1 was carried out except for using 4- (2-propynyl) -2, 3, 5, 6- tetrafluorobenzyl alcohol instead of 2,3,5,6- tetrafluorobenzyl alcohol to obtain 4- (2-propynyl) -2, 3, 5, 6- tetrafluorobenzyl (IR) -cis-3-cyano-2, 2-dimethylcyclopropane carboxylate represented by the following formula:

(hereinafter referred to as the present compound (5)) as a colorless liquid.

¹H-NMR (CDCl₃, TMS) δ (ppm) : 1.28 (s, 3H), 1.46 (s, 3H), 1.77 (d, IH, J = 8.3 Hz), 1.95 (d, IH, J = 8.3 Hz ), 2.07 (t, IH, J = 2.8 Hz), 3.64-3.65 (m, 2H), 5.27 (d, IH, J =12.0 Hz), 5.33 (d, IH, J =12.0 Hz) Production Example 6

The same procedure as that in Production Example 1 was carried out except for using 4 -methylthiomethyl-2, 3, 5, 6- tetrafluorobenzyl alcohol instead of 2,3,5,6- tetrafluorobenzyl alcohol to obtain 4-methylthiomethyl- 2,3,5, β-tetrafluorobenzyl (IR) -cis-3-cyano-2, 2- dimethylcyclopropane carboxylate represented by the following formula:

(hereinafter referred to as the present compound (6)) as a yellow liquid.

¹H-NMR (CDCl₃, TMS) δ (ppm) : 1.28 (s, 3H), 1.46 (s, 3H), 1.77 (d, IH, J = 8.2 Hz), 1.96 (d, IH, J = 8.2 Hz), 2.13 (t, 3H, J = 1.0 Hz), 3.78 (t, 2H, J = 1.0 Hz) 5.26-5.35 (m, 2H) Production Example 7

The same procedure as that in Production Example 1 was carried out except for using 4- (2-propenyl) -2, 3, 5, 6- tetrafluorobenzyl alcohol instead of 2,3,5,6- tetrafluorobenzyl alcohol to obtain 4- (2-propenyl) -2, 3, 5, 6- tetrafluorobenzyl (IR) -cis-3-cyano-2, 2-dimethylcyclopropane carboxylate represented by the following formula:

(hereinafter referred to as the present compound (7)) as a colorless liquid.

¹H-NMR (CDC13, TMS) δ (ppm) : 1.28 (s, 3H), 1.46 (s, 3H), 1.77 (d, IH, J = 8.3 Hz), 1.96 (d, IH, J = 8.3 Hz), 3.47- 3.50 (m, 2H), 5.08-5.13 (m, 2H), 5.25-5.33 (m, 2H), 5.84- 5.94 (m, IH) Production Example 8

The same procedure as that in Production Example 1 is carried out except for using 2, 3, 4 , 5, 6-pentafluorobenzyl alcohol instead of 2, 3, 5, 6-tetrafluorobenzyl alcohol to obtain 2, 3, 4 , 5, 6-pentafluorobenzyl ( IR) -cis-3-cyano-2, 2- dimethylcyclopropane carboxylate represented by the following formula:

(hereinafter referred to as the present compound (8)) .

Next, production of the intermediate for production of the present compound will be described as Reference

Production Examples. Reference Production Example 1

To a solution of 20.2 g of (IS) -cis-2, 2-dimethyl-3- (2- methylpropenyl) cyclopropanecarboxylic acid in 120 itiL of tetrahydrofuran [THF] was added 12.8 g of triethylamine . To the mixture was added dropwise 16.8 g of oxalyl chloride at 0°C, followed by stirring at room temperature for 12 hours. Then, the reaction mixture was poured into 40 g of 28% ammonia water, followed by stirring at room temperature for 2 hours. The reaction mixture was extracted with ethyl acetate, and the organic layer was washed in turn with water and saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 17.5 g of (IS) -cis-2 , 2-dimethyl- 3- (2-methylpropenyl) cyclopropanecarboxamide as a colorless crystal . 1H-NMR (CDCl₃) δ (ppm) : 1.20 (s, 3H), 1.24 (s, 3H), 1.47 (d, IH, J = 8.5 Hz), 1.72 (d, 3H, J = 1.2 Hz), 1.74 (d, IH, J = 8.5 Hz), 1.77 (s, 3H), 5.35-5.38 (m, IH), 5.57 (brs, 2H) Reference Production Example 2

To 11.9 g of (IS) -cis-2, 2-dimethyl-3- (2- methylpropenyl) cyclopropanecarboxamide was added 18.9 mL of acetic anhydride, followed by stirring at room temperature for 30 minutes, and further at 120⁰C for 3.5 hours. The reaction mixture was poured into a mixture of 150 mL of ice water and 120 mL of ethyl acetate, followed by stirring for 1 hour. Then, the organic layer was separated, and the aqueous layer was further extracted with ethyl acetate. The resultant organic layers were combined, and washed in turn with water, an aqueous saturated sodium bicarbonate solution and saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The resultant residue was subjected to silica gel chromatography to obtain 7.02 g of (IS) -cis-2, 2- dimethyl-3- (2-methylpropenyl) cyclopropanecarbonitrile as a light yellow liquid.

¹H-NMR (CDCl₃) δ(ppm) : 1.19 (s, 3H), 1.20 (s, 3H), 1.45 (d, IH, J = 8.5 Hz ), 1.73 (s, 3H), 1.79 (s, 3H), 1.81 (d, IH, J = 8.5 Hz ), 5.01-5.03 (m, IH) Reference Production Example 3

To a mixture of 50 mL of tert-butanol and 130 mL of water was added 1.23 g of (IS) -cis-2 , 2-dimethyl-3- (2- methylpropenyl) cyclopropanecarbonitrile, and 13.0 g of sodium metaperiodate and 210 mg of potassium permanganate were further added thereto, followed by stirring at room temperature for 5 days. The reaction mixture was concentrated under reduced pressure, tert-butanol was distilled off, and the resultant aqueous solution was extracted with ethyl acetate. To the organic layer was added a 5% aqueous solution of potassium carbonate, followed by stirring and further separation into layers. To the resultant aqueous layer was added 5% hydrochloric acid to adjust the pH value to 3, and the aqueous layer was extracted with ethyl acetate. The resultant organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 0.69 g of (IR) -cis-3-cyano-2 , 2-dimethylcyclopropanecarboxylic acid as a colorless liquid.

¹H-NMR (CDCl₃) δ(ppm) : 1.31 (s, 3H), 1.48 (s, 3H), 1.62 (brs, IH), 1.80 (d, IH, J = 8.5 Hz) 1.99 (d, IH, J = 8.5 Hz )

Production Examples of the present compound by the process of the present invention will be described hereinafter. Production Example 9 (Step 1)

To a mixture of 50 mL of tert-butanol and 130 mL of water was added 1.23 g of (IS) -cis-2, 2-dimethyl-3- (2- methylpropenyl) cyclopropanecarbonitrile, and 13.0 g of sodium metaperiodate and 210 mg of potassium permanganate were further added thereto, followed by stirring at room temperature for 5 days. The reaction mixture was concentrated under reduced pressure, tert-butanol was distilled off, and the resultant aqueous solution was extracted with ethyl acetate. The organic layer was added with a 5% aqueous solution of potassium carbonate, followed by stirring and further separation. To the resultant aqueous layer was added 5% hydrochloric acid to adjust the pH value to 3, and the aqueous layer was extracted with ethyl acetate. The resultant organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 0.69 g of (IR) -cis-3-cyano-2, 2- dimethylcyclopropanecarboxylic acid. (Step 2)

Under a nitrogen atmosphere, 182 mg of l-ethyl-3- (3- dimethylaminopropyl) carbodiimide=hydrochloride was added to a mixture of 128 mg of ( IR) -cis-3-cyano-2, 2- dimethylcyclopropanecarboxylic acid prepared in Step 1, 128 mg of 2, 3, 5, 6-tetrafluorobenzyl alcohol, 5 mg of A- dimethylaminopyridine and 5 mL of chloroform, followed by stirring at room temperature for 18 hours. The reaction mixture was added to water, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. To a solution of the residue in 5 mL of anhydrous tetrahydrofuran were added 0.04 mL of acetic anhydride and 5 mg of 4-dimethylaminopyridine, and the resultant mixture was stirred at room temperature for 18 hours to acetylate the remaining benzyl alcohol. To the reaction mixture was added an aqueous saturated sodium bicarbonate, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The resultant residue was subjected to silica gel chromatography to obtain 34 mg of 2,3,5,6- tetrafluorobenzyl= (IR) -cis-3-cyano-2, 2-dimethylcyclopropane carboxylate .

Formulation Examples will be described hereinafter. All the parts are by mass. Formulation Example 1

An emulsifiable concentration is obtained by dissolving 20 parts of any one of the present compounds (1) to (8) in 65 parts of xylene, adding 15 parts of Sorpol 3005X (registered trade name of Toho Chemical Co., Ltd.) thereto, and thoroughly mixing the mixture with stirring. Formulation Example 2

A wettable powder is obtained by adding 5 parts of Sorpol 3005X to 40 parts of any one of the present compounds (1) to (8), thoroughly mixing the mixture, adding 32 parts of Carplex #80 (synthetic hydrated silicon oxide, registered trade name of Sionogi Pharmaceutical Co., Ltd.) and 23 parts of 300 mesh diatomaceous earth thereto, and mixing the mixture with stirring by a juice mixer. Formulation Example 3

After mixing 1.5 parts of any one of the present compounds (1) to (8), 1 part of Tokuseal GUN (synthetic hydrated silicon oxide, manufactured by Tokuyama Corp.), 2 parts of Reax 85A (sodium ligninsulfonate, manufactured by West Vaco Chemicals), 30 parts of Bentonite Fuji (bentonite, manufactured by Hojun Corp.) and 65.5 parts of Shokozan A clay (kaolin clay, manufactured by Shokozan Kogyosho) , the mixed components are thoroughly ground, and water is added thereto. The mixture is thoroughly kneaded, granulated with an extrusion granulator, and dried to obtain 1.5% granules . Formulation Example 4

After mixing 10 parts of any one of the present compounds (1) to (8), 10 parts of phenylxylylethane and 0.5 part of Sumijul L-75 (tolylene diisocyanate, manufactured by Sumitomo Bayer Urethane Ltd.), the mixture is added to 20 parts of a 10% aqueous solution of gum arabic, followed by stirring with a homomixer to obtain an emulsion having a mean particle diameter of 20 μm. The emulsion is further mixed with 2 parts of ethylene glycol and the mixture is stirred in a warm bath at 60⁰C for 24 hours to obtain a microcapsule slurry. Separately, a thickening agent solution is prepared by dispersing 0.2 part of xanthan gum and 1.0 part of Veegum R (aluminum magnesium silicate, manufactured by Sanyo Chemical) in 56.3 parts of ion- exchanged water. A mocrocapsule formulation is obtained by mixing 42.5 parts of the microcapsule slurry and 57.5 parts of the thickening agent solution. Formulation Example 5 After mixing 10 parts of any one of the present compounds (1) to (8) and 10 parts of phenylxylylethane, the mixture is added to 20 parts of a 10% aqueous solution of polyethylene glycol, followed by stirring with a homomixer to obtain an emulsion having a mean particle diameter of 3 μm. Separately, a thickening agent solution is prepared by dispersing 0.2 part of xanthan gum and 1.0 part of Veegum R (aluminum magnesium silicate, manufactured by Sanyo Chemical) in 58.8 parts of ion-exchanged water. A flowable formulation is obtained by mixing 40 parts of the emulsion and 60 parts of the thickening agent solution. Formulation Example 6

Dust is obtained by mixing 5 parts of any one of the present compounds (1) to (8), 3 parts of Carplex #80 (synthetic hydrated silicon oxide, registered trade name of Sionogi Pharmaceutical Co., Ltd.), 0.3 part of PAP (a mixture of monoisopropyl phosphate and diisopropyl phosphate) and 91.7 parts of talc (300 mesh) with stirring by a juice mixer. Formulation Example 7 An oil solution is obtained by dissolving 0.1 part of any one of the present compounds (1) to (8) in 10 parts of dichloromethane, and adding 89.9 parts of deodorized kerosene thereto. Formulation Example 8 An oil aerosol is obtained by mixing and dissolving 1 part of any one of the present compounds (1) to (8), 5 parts of dichloromethane and 34 parts of deodorized kerosene, filling the resultant solution in an aerosol vessel, attaching a valve to the vessel, and charging the vessel with 60 parts of a propellent (liquefied petroleum gas) under pressure through the valve. Formulation Example 9

An aqueous aerosol is obtained by mixing and dissolving 0.6 part of any one of the present compounds (1) to (8), 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of sorbitan monolaurate (Leodol SP-LlO, manufactured by Kao Co., Ltd., HLB: 8.6), filling the resultant solution and 50 parts of water in an aerosol vessel, attaching a valve to the vessel, and charging the vessel with 40 parts of a propellent (liquefied petroleum gas) under pressure through the valve. Formulation Example 10

An pesticidal incense is obtained by dissolving 0.3 g of any one of the present compounds (1) to (8) in 20 mL of acetone, uniformly mixing the solution and 99.7 g of a base material for an incense (a mixture of an incense material powder, lees flour and wood flour in a ratio of 4:3:3), adding 100 mL of water thereto, thoroughly kneading the mixture, and molding and drying the mixture. Formulation Example 11

An electric pesticidal mat is obtained by dissolving 0.8 g of any one of the present compounds (1) to (8) and 0.4 g of piperonyl butoxide in acetone, adjusting the total volume to 10 mL, and uniformly impregnating 0.5 mL of the solution in a base material (in a plate form, obtained by- hardening fiber comprised of cotton linter and pulp) for an electric insecticide mat of 2.5 cm x 1.5 cm and 0.3 cm thick.

Formulation Example 12 A part for a liquid absorbing core-type heat transpiration device is obtained by dissolving 3 parts of any one of the present compounds (1) to (8) in 97 parts of deodorized kerosene, placing the solution in a vessel made of vinyl chloride, and inserting a liquid-absorbing core (prepared by solidifying an inorganic powder with a binder, followed by sintering it) whose upper part can be heated by a heater into the vessel. Formulation Example 13

A heat fumigant is obtained by dissolving 100 mg of any one of the present compounds in an appropriate amount of acetone, and impregnating in a porous ceramic plate of

4.0 cm x 4.0 cm and 1.2 cm thick. Formulation Example 14

A room-temperature-volatilizing formulation is obtained by dissolving 100 μg of any one of the present compounds (1) to (8) in an appropriate amount of acetone, uniformly applying the solution on a filter paper of 2 cm x 2 cm and 0.3 mm thick, and air-drying to remove acetone.

Test Examples showing the effectiveness of the present compound as an active ingredient for a pest controlling composition will be described hereinafter.

The present compounds (1) to (6) were used as the test compounds in Test Example 1, and the present compound (7) was used in Test Example 2. In the Test Examples, the following compounds were also used as comparative control compounds. 2,3,5, 6-tetrafluorobenzyl (IR) -trans-3- (2-methyl-l- propenyl) -2, 2-dimethylcyclopropanecarboxylate described in JP 05-32509 A, hereinafter referred to as the comparative compound (A) , 4-methoxy-2, 3, 5, 6-tetrafluorobenzyl (IR) -trans-3- (2-methyl- 1-propenyl) -2, 2-dimethylcyclopropanecarboxylate described in JP 11-222463 A, hereinafter referred to as a comparative compound (B) , 4-methoxymethyl-2, 3, 5, 6-tetrafluorobenzyl (IR) -trans-3- (2- methyl-1-propenyl ) -2 , 2-dimethylcyclopropanecarboxylate described in JP 2001-11022 A, hereinafter referred to as a comparative compound (C) , 4- (2-propynyl) -2,3,5, 6-tetrafluorobenzyl (IR) -trans-3- (2- methyl-1-propenyl) -2, 2-dimethylcyclopropanecarboxylate described in JP 61-207361 A, hereinafter referred to as a comparative compound (D),

4-methylthiomethyl-2, 3,5, 6-tetrafluorobenzyl (IR) -trans-Z- 3- (2-chloro-3, 3, 3-trifluoromethyl-1-propenyl) -2,2- dimethylcyclopropanecarboxylate described in JP 57-123146 A, hereinafter referred to as a comparative compound (E) , and 5-benzylfuran-3-ylmethyl (IR) -trans-3- (2-methyl-l- propenyl) -2, 2-dimethylcyclopropanecarboxylate described in Pestic. Sci. 1976. 7, 492-498, hereinafter referred to as a comparative compound (X) . Test Example 1

A 0.025% oil solution was prepared by dissolving 0.025 part of the test compound in 10 parts of dichloromethane, and the solution was mixed with 89.975 parts of deodorized kerosene. Ten Blattella germanica (5 males and 5 females, respectively) were released in a test container (8.75 cm in diameter, 7.5 cm in height, with wire netting of 16 mesh at the bottom) with butter spread on the inside wall. The container was placed on the bottom of a test chamber (bottom: 46 cm x 46 cm, height: 70 cm) . From 60 cm above the upper surface of the container, 1.5 mL of the above prepared oil agent was sprayed with a spray gun (atomizing pressure of 0.4 kg/cm²) . One container was sprayed with one kind of the oil solution. The container was taken out of the test chamber 30 seconds after spraying. After standing a given period of time (after 2 minutes), the number of the insects knocked down was counted (mean value of two replications) . The results are shown in Table 1. Table 1

The number of insects

Test compound knocked down after 2 minutes

Present compound (1) 7

Present compound (2) 7

Present compound (3) 9

Present compound (4) 10

Present compound (5) 10

Present compound (6) 10

Comparative compound (A) 0

Comparative compound (B) 0

Comparative compound (C) 2

Comparative compound (D) 4

Comparative compound (E) 0

Comparative compound (X) 0 Text Example 2

The test compound was dissolved in a mixed solvent of an isoparaffin organic solvent (Isopar M, manufactured by Exxon) and dichloromethane in a ratio of 9:1 to prepare a 0.025% oil solution.

Twenty Musca domestics were released in a cubic chamber whose sides were 70 cm, respectively. From a small window on the side wall of the chamber, 0.7 mL of the prepared oil solution was sprayed into the chamber at a pressure of 88 x 10⁴ Pa with a spray gun. Then, after a given period of time (after 5 minutes) , the number of the insects knocked down was counted (mean value of two replications) . The results are shown in Table 2. Table 2

Industrial Applicability

Since the present compound has an excellent pest controlling effect, it is useful as an active ingredient of a pest controlling composition.

Claims

1 . A cyclopropanecarboxylate of the formula ( 1 ) :

wherein R¹ represents a hydrogen atom, a fluorine atom, a C1-C4 alkyl group, a C2-C4 alkenyl group, a C2-C4 alkynyl group, a C1-C4 alkoxy group, a (C1-C4 alkyl) oxymethyl group or a (C1-C4 alkyl) thiomethyl group.

2. The cyclopropanecarboxylate according to claim 1, wherein R¹ is a hydrogen atom, a fluorine atom, a methyl group, a 2-propenyl group, a 2-propynyl group, a methoxy group, a methoxymethyl group or a methylthiomethyl group.

3. A pest controlling composition, which comprises the cyclopropanecarboxylate according to claim 1 or 2 as an active ingredient.

4. A pest controlling method, which comprises applying an effective amount of the cyclopropanecarboxylate according to claim 1 or 2 to a pest or a habitat of the pest .

5. A process for producing the cyclopropanecarboxylate according to claim 1 or 2 , which comprises the steps of reacting a compound of the formula (6) :

with a periodate in the presence of an oxide of manganese or ruthenium to obtain a carboxylic acid of the formula (3) :

and reacting the carboxylic acid of the formula (3) with an alcohol of the formula (2) :

wherein R¹ represents a hydrogen atom, a fluorine atom, a

C1-C4 alkyl group, a C2-C4 alkenyl group, a C2-C4 alkynyl group, a C1-C4 alkoxy group, a (C1-C4 alkyl) oxymethyl group or a (C1-C4 alkyl) thiomethyl group, to obtain the cyclopropanecarboxylate .