DESCRIPTION CYCLOPROPANECARBOXYLIC ACID ESTERS AND THEIR USE AS PEST CONTROL AGENTS

Technical Field The present invention relates to an ester compound and use thereof.

Background Art

Conventionally, various compounds have been developed to control pests (See, The Second series of pharmaceutical research and development, vol.18, "Development of agrochemicals III", page 493, Hirokawa Shoten, 1993) . For example, Japanese Published Examined Application S39-4074 describes a certain kind of cyclopropanecarboxylate derivatives.

Disclosure of the Invention

The present invention has an object of providing a novel compound having an excellent pest controlling effect. The present inventors have intensively studied and resultantly found that a compound of the formula (1) has an excellent pest controlling effect, leading to the present invention.

The present invention provides an ester compound of formula (1) :

(hereinafter referred to as the present compound) , a pest controlling composition comprising the present compound as an active ingredient, and a pest controlling method comprising a step of applying an effective amount of the present compound to a pest or a habitat of the pest.

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

Embodiments for Carrying Out the Invention

The present compound has isomers ascribable to one asymmetric carbon atom on the cyclopentenolone ring and two asymmetric carbon atoms on the cyclopropane ring, as well as isomers ascribable to the double bond presented in - CH=C(CN)CH ₃ moiety. The present invention includes the above-mentioned isomers which have a pest controlling activity and the mixtures of them.

The present compound includes, for example, the following compounds.

A compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopropane ring is R- configuration; A compound of the formula (1) wherein the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is trans configuration;

A compound of the formula (1) wherein the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is cis configuration;

A compound of the formula (1) wherein the relative configuration of the double bond presented in -CH=C(CN)CH ₃ moiety is Z-configuration; A compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopropane ring is R- configuration, and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration; A compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopropane ring is R- configuration, and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is cis configuration; A compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopropane ring is R- configuration, the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration, and the relative configuration of the double bond presented in -CH=C(CN)CH ₃ moiety is Z- configuration;

A compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopropane ring is R- configuration, the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is cis configuration, and the relative configuration of the double bond presented in -CH=C(CN)CH ₃ moiety is Z- configuration;

A compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopentenolone ring is S-configuration;

A compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopentenolone ring is S-configuration and the absolute configuration at 1- position of the cyclopropane ring is R-configuration;

A compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopentenolone ring is S-configuration and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration;

A compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopentenolone ring is S-configuration and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is cis configuration;

A compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopentenolone ring is S-configuration and the relative configuration of the double bond presented in -CH=C(CN)CH ₃ moiety is Z- configuration;

A compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopentenolone ring is S-configuration, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration;

A compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopentenolone ring is S-configuration, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is cis configuration; A compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopentenolone ring is S-configuration, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is trans configuration, and the relative configuration of the double bond presented in -CH=C(CN)CH ₃ moiety is Z-configuration;

A compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopentenolone ring is S-configuration, the absolute configuration at 1-position of the cyclopropane ring is R-configuration, the relative configuration of substituents at the 1-position and the 3- position on the cyclopropane ring is cis configuration, and the relative configuration of the double bond presented in -CH=C(CN)CH ₃ moiety is Z-configuration;

The mixture of the isomers includes, for example, the following ones.

A mixture containing, in an amount of 50 % or more of them, the compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopropane ring is reconfiguration and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration; A mixture containing, in an amount of 80 % or more of them, the compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopropane ring is R- configuration and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration;

A mixture containing, in an amount of 90 % or more of them, the compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopropane ring is R- configuration and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration;

A mixture containing, in an amount of 50 % or more of them, the compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopentenolone ring is S-configuration, the absolute configuration at 1-position of the cyclopropane ring is R-configuration and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration; A mixture containing, in an amount of 80 % or more of them, the compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopentenolone ring is S-configuration, the absolute configuration at 1-position of the cyclopropane ring is R-configuration and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration; and

A mixture containing, in an amount of 90 % or more of them, the compound of the formula (1) wherein the absolute configuration at 1-position of the cyclopentenolone ring is S-configuration, the absolute configuration at 1-position of the cyclopropane ring is R-configuration and the relative configuration of substituents at the 1-position and the 3-position on the cyclopropane ring is trans configuration.

The present compound can be produced by reacting the compound of the formula (2)

with the compound of the formula (3)

or a reactive derivative of the compound of the formula (3)

The reactive derivative includes acid halides of the compound of the formula (3), acid anhydrides of the compound, or methyl esters of the compound. The acid halide includes acid chloride compounds and acid bromide compounds .

The reaction is carried out usually in a solvent in the presence of a condensing agent or base.

The condensing agent or base is appropriately selected depending on the kind of the compound of the formula (3) or reactive derivative thereof.

Examples of the solvent include hydrocarbons such as benzene, toluene or hexane, ethers such as diethyl ether, or tetrahydrofuran, and halogenated hydrocarbons such as chloroform, dichloromethane, or 1, 2-dichloroethane, chlorobenzene, and mixtures of them.

Examples of the condensing agent include dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3- ethylcarbodiimide hydrochloride. Examples of the base include organic bases such as triethylamine, pyridine, N, N-diethylaniline, 4- dimethylaminopyridine, or diisopropylethylamine.

The reaction time is usually in the range of 5 minutes to 72 hours. The reaction temperature is usually in the range of -

2O ⁰ C to 100°C, and preferably in the range of -5°C to 100 ⁰ C. Here, the reaction temperature is in the range of -

20 ⁰ C to the boiling point of the solvent, preferably in the range of -5°C to the boiling point of the solvent, when the boiling point of the solvent to be used is lower than 100 ⁰ C. In the reaction, the ^' molar ratio of the compound of the formula (2) to the compound of the formula (3) or reactive derivative thereof can be arbitrarily selected, however, it is preferably equimolar or near ratio. The condensing agent or base can be used usually at any proportion from 0.25 mol to excess amount, preferably 0.5 mol to 5 mol, with respect to 1 mol of the compound of the formula (2 ) .

After completion of the reaction, the reaction mixture is filtrated and the filtrate is concentrated, alternatively, the reaction mixture is poured into water, then, usual post-treatment operations such as extraction with organic solvent, or concentration are performed, thus, the present compound can be obtained. The resultant present compound can be purified by operations such as chromatography, or distillation.

The compound of the formula (2) is a commercially available.

The compound of the formula (3) is described in Agr. Biol. Chem., 34, page 1119 (1970) and the like, alternatively, can be produced by the methods described in the document .

The pests on which the present compound manifests an effect include, for example, arthropods such as insects, or mites .

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, Autographa , and Agrotis spp. such as Agrotis segetum and Agrotis ipsilon, Helicoverpa spp. , Heliothis spp. , Plutella xylostella, Parnara guttata, Tinea translucens, and Tineola bisselliella,

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 antique, Tephritidae, Liriomyza sa-tivae, Agromyzidae,

Drosophilidae, Psychodidae, Phoridae, Tabanidae, Simuliidae, Stomoxyidae, and Ceratopogonidae,

Blattaria :

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

Hymenoptera :

Formicidae, Vespidae, Bethylidae, Tenthredinidae such as Athalia rosae ruficornis, 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 Rootworms 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, and Paederus fuscipes, etc. Thysanoptera :

Thrips palmi, Frankliniella occidentalis, Thrips hawaiiensis, 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 longiconis, Dermanyssidae such as Ornithonyssus sylviarum and Dermanyssus gallinae.

The pest controlling composition of the present invention is usually a formulation, which may consist of the present compound itself.

Examples of the formulation form include an oil solution, an emulsifiable concentrate, a wettable powder, a flowable formulation (e.g., an aqueous suspension, or an aqueous emulsion) , a microcapsule, a dust, a granule, a tablet, an aerosol, a carbon dioxide formulation, a heat transpiration formulation (e.g., an insecticidal coil, an electric insecticidal mat, or a liquid absorbing core-type heat transpiration pesticide) , a piezo insecticidal formulation, a heat fumigant (e.g., a self combustion-type fumigant, a chemical reaction-type fumigant, or a porous ceramic plate fumigant) , an unheated transpiration formulation (e.g., a resin transpiration formulation, a paper transpiration formulation, an unwoven fabric transpiration formulation, a knit fabric transpiration formulation, or a sublimating tablet) , an aerosol formulation (e.g., a fogging formulation), a direct contact formulation (e.g., a sheet-shaped contact formulation, a tape-shaped contact formulation, or a net-shaped contact formulation), an ULV formulation and a poison bait. These formulations contain, depending on the formulation form, the present compound usually in an amount of 0.001 to 98% by weight of the total amount.

The formulation forms as mentioned above can be prepared by, for example, the following methods. [1] A method which comprises mixing the present compound with a solid carrier, liquid carrier, gaseous carrier, bait and the like, and if necessary, adding a surfactant or other formulation auxiliary substances and then processing. [2] A method which comprises impregnating the present compound in a base material.

[3] A method which comprises mixing the present compound and a base material, and then molding the resulting mixture. Examples of the solid carrier for the formulation include fine powders or granules of clays (e.g., kaolin clay, diatomaceous earth, bentonite, Fubasami clay, or acid white clay) , synthetic hydrated silicon oxide, talc, ceramics, other inorganic minerals (e.g., sericite, quartz, sulfur, active carbon, calcium carbonate, or hydrated silica) and chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium chloride, or urea); substances that are solid at room temperature (e.g., 2, 4, 6-triisopropyl-l, 3, 5-trioxane, naphthalene, p- dichlorobenzene, camphor, or adamantine) ; and felt, fiber, fabric, knit, sheet, paper, thread, foam, porous material and multi-filament comprising one or more substances selected from the group consisting of wool, silk, cotton, hemp, pulp, synthetic resins (e.g., polyethylene resins such as low density polyethylene, straight chain low density polyethylene and high density polyethylene; ethylene-vinyl ester copolymers such as an ethylene-vinyl acetate copolymer; ethylene-methacrylate copolymers such as an ethylene-methyl methacrylate copolymer and an ethylene- ethyl methacrylate copolymer; ethylene-acrylate copolymers such as an ethylene-methyl acrylate copolymer and an ethylene-ethyl acrylate copolymer; ethylene-vinylcarboxylic acid copolymers such as an ethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymers; polypropylene resins such as a propylene homopolymer and a propylene- ethylene copolymer; poly-4-methylpentene-l, polybutene-1, polybutadiene, polystyrene; acrylonitrile-styrene resin; acrylonitrile-butadiene-styrene resins; styrene elastomers such as a styrene-conjugated diene block copolymer and a hydrogenated styrene-conjugated diene block copolymer; fluorine resins; acrylic resins such as methyl polymethacrylate; polyamide resins such as nylon 6 and nylon 66; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate and polycyclohexylene dimethylene terephthalate; or porous resins such as polycarbonate, polyacetal, . polyacryl sulfone, polyarylate, hydroxybenzoic acid polyester, polyetherimide, polyester carbonate, polyphenylene ether resins, polyvinyl chloride, polyvinylidene chloride, polyurethane, foamed polyurethane, foamed polypropylene and foamed ethylene) , glass, metal and ceramics .

Examples of the liquid carrier include aromatic or aliphatic hydrocarbons (e.g., xylene, toluene, alkylnaphthalene, phenylxylylethane, kerosene, light oil, hexane, or cyclohexane) , halogenated hydrocarbons (e.g., chlorobenzene, dichloromethane, dichloroethane, or trichloroethane) , alcohols (e.g., methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, or ethylene glycol), ethers (e.g., diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran, or dioxane) , esters (e.g., ethyl acetate, or butyl acetate), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone) , nitriles (e.g., acetonitrile, or isobutyronitrile) , sulfoxides (e.g., dimethyl sulfoxide), acid amides (e.g., N, N-dimethylformamide, N, N- dimethylacetamide, or N-methyl-pyrrolidone) , alkylidene carbonate (e.g., propylene carbonate), vegetable oils (e.g., soybean oil, or cottonseed oil), plant essential oils (e.g., orange oil, hyssop oil, or lemon oil) , 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 sulfate, 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 formulation include a binder, a dispersant and a stabilizer. Specifically, there are, for example, casein, gelatin, polysaccharides (e.g., starch, gum arabic, cellulose derivatives, or alginic acid) , lignin derivatives, bentonite, saccharides, synthetic water-soluble polymers (e.g., polyvinyl alcohol, or polyvinyl pyrrolidone) , polyacrylic acid, BHT (2, 6-di-tert-butyl-4-methylphenol) and BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3- tert-butyl-4-methoxyphenol) . Examples of a base material for the insecticidal coil include a mixture of vegetable powder such as wood flour and lees powder, and a binder such as incense material powder, starch and gluten. Examples of a base material for the electric insecticidal mat include a plate obtained by hardening cotton linter and a plate obtained by hardening fibrils of a mixture of cotton linter and pulp.

Examples of a base material for the self combustion- type fumigant include combustible exothermic agents such as nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethylcellulose and wood flour, thermal decomposition stimulants such as alkali metal salt, alkaline earth metal salt, dichromate and chromate, oxygen carriers such as potassium nitrate, combustion-supporting agents such as melamine and flour starch, extenders such as diatomaceous earth, and binders such as synthetic glue.

Examples of a base material for the chemical reaction-type fumigant include exothermic agents such as alkali metal sulfide, polysulfide, hydrosulfide and calcium oxide, catalytic agents such as a carbonaceous material, iron carbide and active white clay, organic foaming agents such as azodicarbonamide, benzenesulfonylhydrazide, dinitropentamethylenetetramine, polystyrene and polyurethane, and fillers such as strips of natural fiber and synthetic fiber.

Examples of a base material resin for resin transpiration formulations include polyethylene resins such as low density polyethylene, straight chain low density polyethylene and high density polyethylene; ethylene-vinyl ester copolymers such as an ethylene-vinyl acetate copolymer; ethylene-methacrylate copolymers such as an ethylene-methyl methacrylate copolymer and an ethylene- ethyl methacrylate copolymer; ethylene-acrylate copolymers such as an ethylene-methyl acrylate copolymer and an ethylene-ethyl acrylate copolymer; ethylene-vinylcarboxylic acid copolymers such as an ethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymers; polypropylene resins such as a propylene copolymer and a propylene- ethylene copolymer; poly-4-methylpentene-l, polybutene-1, polybutadiene, polystyrene, acrylonitrile-styrene resin; s acrylonitrile-butadiene-styrene resins; styrene elastomers such as a styrene-conjugated diene block copolymer and a hydrogenated styrene-conjugated diene block copolymer; fluorine resins; acrylic resins such as methyl polymethacrylate; 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, polyarylate, hydroxybenzoic acid polyester, polyetherimide, polyester carbonate, polyphenylene ether resin, polyvinyl chloride, polyvinylidene chloride and polyurethane .

These base material resins may be used alone or as a combination of two or more kinds. If necessary, a plasticizer such as phthalate (e.g., dimethyl phthalate, or dioctyl phthalate) , adipic acid esters and stearic acid may be added to these base materials.

The resin transpiration formulations can be prepared by mixing the present compound with the base material, kneading the mixture, followed by molding it by injection molding, extrusion molding or pressure molding.

The resultant resin transpiration formulations 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 can be processed into animal collars, animal ear tags, sheet products, trap strings, gardening supports and other products.

Examples of a base material for the poison bait include 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 comprises a step of applying an effective amount of the present compound to a pest or a habitat of the pest. In the controlling method, the present compound is usually applied, in the form of a pest controlling composition, to a pest or a habitat of the pest.

The application of the present compound can be carried out, for example, according to the following methods, and specific application methods can be appropriately selected depending on the form of the present compound, place to be used thereof, and the like.

(1) A method which comprises treating a pest or habitat of the pest with the present compound or the pest controlling composition of the present invention as it is. (2) A method which comprises diluting the present compound or the pest controlling composition of the present invention with a solvent such as water, and then spraying it on a pest or habitat of the pest. In the method (2), the present compound or a pest controlling composition of the present invention is generally diluted so that the concentration of the present compound is 0.1 to 10000 ppm, and then sprayed.

(3) A method which comprises heating a pest controlling composition of the present invention at a habitat of the pest to volatilize the present compound.

In the method (3), both the application amount and the application concentration of the present compound can be appropriately selected depending on the form of the present compound, application time, application place, application method, the kind of pests, injury conditions and the like.

When the present compound is used for prevention of epidemics, its application amount is usually 0.0001 to 1000 mg/m ³ when applied in space, and 0.0001 to 1000 mg/m ² when applied on plane.

A heat fumigant such as an insecticidal stick, electric insecticidal mat can be applied by volatilizing an active ingredient by heating according to its formulation form. A unheated transpiration formulation such as resin transpiration formulation, a paper transpiration formulation, an unwoven fabric transpiration formulation, a knit fabric transpiration formulation, or a sublimating tablet can be applied, for example, by placing as it is in a space to be applied, or placing the formulation under an influence of blowing air.

In the case where the present compound is applied for the purpose of prevention of epidemics, examples of the habitat of a pest include a closet, a Japanese cabinet, a Japanese chest, a cupboard, a toilet, a bathroom, a shed, a living room, a dining room, a garage and the interior of a car. The present compound can be also applied to outdoor open space.

The present compound can be used on animals by a known method in the veterinary field, when used for controlling external parasites of livestock such as cow, horse, pig, sheep, goat, or chicken, or small animals such as dog, cat, rat, or mouse.

As specific use methods, when intended for systemic control, for example, table, feedstuff mixing, suppository and injection (intramuscular, subcutaneous, intravenous, intraperitoneal) are used for administration. When intended for non-systemic control, for example, the present compounds are applied by such a method as spraying of oil or aqueous liquid, pour-on treatment, spot-on treatment, washing animal with a shampoo formulation, forming a resin transpiration formulation into collar or ear tag to be fixed on animal. The amount of the present compound when administered to animal is usually in the, range of 0.01 to 1000 mg with respect to 1 kg of body weight of animal.

The present compound can be used in admixture or together with other insecticides, acaricides, nematicides, soil pest controlling agents, bactericides, herbicides, plant growth regulators, repellents, synergists, fertilizers or soil improving agents. The kinds of the above-described insecticides, acaricides, nematicides, soil pest controlling agents, bactericides, herbicides, plant growth regulators, repellents, synergists, fertilizers and soil improving agents are not particularly restricted.

Examples of active ingredients of such insecticides and miticides include organophosphorus compounds such as fenitrothion, fenthion, diazinon, chlorpyrifos, acephate, methidathion, disulfoton, DDVP, sulprofos, cyanophos, dioxabenzofos, dimethoate, phenthoate, malathion, trichlorphon, azinphosmethyl, monocrotophos, or ethion; carbamate compounds such as BPMC, benfuracarb, propoxur, carbosulfan, carbaryl, methomyl, ethiofencarb, aldicarb, oxamyl, or fenothiocarb; pyrethroid compounds such as ethofenprox, fenvalerate, esfenvalerate, fenpropathrin, cypermethrin, permethrin, cyhalothrin, ^' deltamethrin, cycloprothrin, fluvalinate, bifenthrin, 2-methyl-2- (4- bromodifluoromethoxyphenyl) propyl (3-phenoxybenzyl) ether, tralomethrin, silafluofen, d-phenothrin, cyphenothrin, d- resmethrin, acrinathrin, cyfluthrin, tefluthrin, transfluthrin, tetramethrin, allethrin, d-furamethrin, prallethrin, imiprothrin, empenthrin, 5- (2- propynyl ) furfuryl 2,2,3, 3-tetramethylcyclopropane carboxylate, metofluthrin, profluthrin, and dimefluthrin; nitroimidazolidine derivatives, nitroguanidine derivatives such as clothianidin and dinotefuran, N- cyanoamidine derivatives such as acetamiprid, chlorinated hydrocarbon compounds such as endosulfan, γ-BHC, and 1- bis (chlorophenyl) -2, 2, 2-trichloroethanol, benzoylphenylurea compounds such as chlorfluazuron, teflubenzuron, and flufenoxuron, phenylpyrazole compounds, and metoxadiazone, bromopropylate, tetradifon, chinomethionat, pyridaben, fenpyroximate, diafenthiuron, tebufenpyrad, polynactin complexes (tetranactin, dinactin, trinactin) , pyrimidifen, milbemectin, abamectin, ivermectin, and azadirachtin. 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-menthane-3, 8- diol and vegetable essential oils 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 α- [2- (2-butoxyethoxy) ethoxy] -4, 5- methylenedioxy-2-propyltoluene (piperonyl butoxide) .

EXAMPLES

The present invention will be illustrated further in detail by production examples, formulation examples and test examples, but the present invention is not limited to these examples.

First, production examples of the present compound are shown.

Production Example 1

Into 15 m'l chloroform solution containing 251 mg (1.67 mmol) of (4S) -hydroxymethyl-3-methyl-2- (2-propynyl) - 2-cyclopentenone and 200 mg (1.15 mmol) of (IR) -trans-3- ((Z) -2-cyano-l-propenyl) -2, 2-dimethylcyclopropane carboxylic acid, 320 mg (1.67 mmol) of l-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride and 5 mg of 4-methylaminopyridine were added. The obtained mixture was stirred at room temperature for 18 hours. Water was poured into the reaction mixture, and then the reactant was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, then, concentrated under reduced pressure condition, and the resulting residue was subjected to silica gel column chromatography, to give 257 mg of (Is) -2-methyl-4-oxo-3- (2-propynyl) -2-cyclopentenyl (IR) - trans-3- ( (z) -2-cyano-l-propenyl) -2, 2-dimethylcyclopropane carboxylate (hereinafter, referred to as the present compound (I)) of the following formula.

Present compou nd ( 1 )

¹ H-NMR(CDCl ₃ ,TMS) δ (ppm) : 1.22 (s, 3H) , 1.33(s,3H) ,

1.74 (d,lH,J = 5.1Hz) , 1.97 (d,3H,J = 1.4Hz) , 1.99(t,lH,J = 2.9Hz) , 2.18(s, 3H) , 2.26 (dd, IH, J=18.7, 2.9Hz) , 2- 47 (dd, IH, J =9.5, 5. IHz) , 2.91 (dd, IH, J=18.7, 6.3Hz) , 3.16(s,2H) , 5.71 (d,lH,J = 6.3 Hz) , 5.84 (dd, IH, J=9.4,1.4 Hz)

Next, Formulation Examples will be shown. Parts are by weight.

Formulation Example 1 An emulsifiable concentration is obtained by dissolving 20 parts of the present compound 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 the present compound, 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

A mixture of 1.5 parts of the present compound, 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) are thoroughly ground, and water is added thereto. The mixture is then thoroughly kneaded, granulated with an extrusion granulator, and dried to obtain a 1.5% granule.

Formulation Example 4

Ten (10) parts of the present compound, 10 parts of phenylxylylethane and 0.5 part of Sumijul L-75 (tolylene diisocyanate, manufactured by Sumitomo Bayer Urethane Ltd. ) are mixed. The obtained 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 60°C for 24 hours to obtain 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 microcapsule formulation is obtained by mixing 42.5 parts of the microcapsule slurry and 57.5 parts of the thickening agent solution.

Formulation Example 5

A mixture of 10 parts of the present compound and 10 parts of phenylxylylethane 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 above emulsion and 60 parts of the thickening agent solution.

Formulation Example 6

A dust is obtained by mixing 5 parts of the present compound, 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 the present compound in 10 parts of dichloromethane, and mixing the solution with 89.9 parts of deodorized kerosene.

Formulation Example 8

An oil aerosol is obtained by mixing and dissolving 1 part of the present compound, 5 parts of dichloromethane and 34 parts of deodorized kerosene, filling an aerosol vessel with the resultant solution, 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 the present compound, 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of Atmos 300 (emulsifier, registered trademark of Atlas Chemical Inc.), filling an aerosol vessel with the resultant solution and 50 parts of water, 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 insecticidal coil is obtained by dissolving 0.3 g of the present compound in 20 mL of acetone, uniformly mixing and stirring the solution and 99.7 g of a base material for an insecticidal coil (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 insecticidal mat is obtained by dissolving 0.8 g of the present compound and 0.4 g of piperonyl butoxide in acetone to obtain 10 mL of the solution, and uniformly impregnating, with 0.5 mL of the solution, a base material (in a plate form, obtained by hardening fibrils comprised of a mixture of cotton linter and pulp) for an electric insecticidal mat of 2.5 cm x 1.5 cm and 0.3 cm thick.

Formulation Example 12

A part to be used for a liquid absorbing core-type heat transpiration device is obtained by dissolving 3 parts of the present compound in 97 parts of deodorized kerosene, placing the resultant solution in a vessel made of vinyl chloride, and inserting a liquid-absorbing core into the vessel. The liquid-absorbing core is prepared by solidifying an inorganic powder with a binder, followed by sintering it, upper part of which can be heated by a heater,

Formulation Example 13 A heat fumigant is obtained by dissolving 100 mg of the present compound in an appropriate amount of acetone, and impregnating a porous ceramic plate of 4.0 cm x 4.0 cm and 1.2 cm thick with the solution.

Formulation Example 14

A room-temperature-volatilizing formulation is obtained by dissolving 100 μg of the present compound in an appropriate amount of acetone, uniformly applying the solution onto a filter paper of 2 cm x 2 cm and 0.3 mm thick, and air-drying to remove acetone.

The following test examples show that the present compound is effective as an active ingredient of a pest controlling composition.

Test Example 1

A solution of 0.1 part of the present compound in 10 parts of dichloromethane was mixed with 89.9 parts of deodorized kerosene to give a 0.1% oil solution.

Six (6) adult American cockroaches (3 males and 3 females) were left in a metal container (diameter 12.5cm, 10 cm high) , the bottom face of which was made of 16 mesh metallic wire and the inner face of which was smothered in butter. The container containing the American cockroaches was set at the bottom of a chamber (46 cm x 46 cm, 70 cm high) .

The oil solution (1.5 ml) was sprayed with a spray gun at a pressure of 0.4 kg/cm ² from 60 cm higher than the upper face of the container. The container was pulled out from the chamber 30 seconds after the spraying. Then the number of knocked-down cockroaches was counted.

The procedure was duplicated for other American cockroaches.

For comparison, the same test as test example 1, except that container was pulled out from the chamber 2 minutes after the spraying, was conducted respectively for the compound of the following formula (A)

(the compound described in Japanese Published Examined Application S39-4074, hereinafter, referred to as comparative compound (A) ) and

(the compound described in Japanese Application H03-206008, hereinafter, referred to as comparative compound (B) ) . The results are shown in Table 1. Table 1

Industrial Applicability

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