JP2010173953A - Cyclopropanecarboxylic acid ester and application thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound having excellent pest-controlling activity. <P>SOLUTION: The cyclopropanecarboxylic acid ester is represented by formula (1). The pest-controlling agent contains the cyclopropanecarboxylic acid ester represented by formula (1) as an active ingredient. The method for controlling the pest includes applying an effective amount of the cyclopropanecarboxylic acid ester represented by formula (1) to the pest or to the habitat of the pest. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a cyclopropanecarboxylic acid ester and use thereof.

  Conventionally, various compounds have been synthesized in order to control pests (see, for example, Non-Patent Document 1). For example, Patent Document 1 describes certain types of cyclopropanecarboxylic acid ester derivatives. However, the cyclopropanecarboxylic acid ester derivatives described have not always had sufficient pest control efficacy.

Japanese Examined Patent Publication No. 39-4074

“Continued Drug Development Volume 18: Development of Pesticides III”, Yodogawa Shoten, 1993, p. 493

  An object of the present invention is to provide a novel compound having an excellent pest control effect.

で示されるシクロプロパンカルボン酸エステル（以下、本発明化合物と記す。）；本発明化合物を有効成分として含有することを特徴とする有害生物防除剤；及び、本発明化合物の有効量を有害生物又は有害生物の生息場所に施用することを特徴とする有害生物防除方法を提供する。 As a result of intensive studies, the present inventors have found that the ester compound represented by the following formula (1) has an excellent pest control effect, and have reached the present invention.
That is, Formula (1)

And a pest control agent characterized by containing the compound of the present invention as an active ingredient; and an effective amount of the compound of the present invention as a pest or A pest control method characterized by being applied to a pest habitat is provided.

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

  The compound of the present invention has one isomer derived from a cyclopentenolone ring, two isomers derived from two asymmetric carbon atoms present on the cyclopropane ring, and an isomer derived from a double bond. The present invention includes each isomer having activity and a mixture of isomers in any ratio.

Examples of the form of the compound of the present invention include the following.
In the formula (1), a compound wherein the absolute configuration at the 1-position of the cyclopropane ring is an R configuration;
In the formula (1), a compound in which the relative configuration of the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a trans configuration;
In the formula (1), a compound in which the relative configuration of the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a cis configuration;
In the formula (1), a compound in which the relative configuration of a double bond present in the substituent at the 3-position of the cyclopropane ring is the Z configuration;
In the formula (1), a compound in which the absolute configuration at the 1-position of the cyclopropane ring is an R configuration, and the relative configuration of the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is trans;
In the formula (1), a compound in which the absolute configuration at the 1-position of the cyclopropane ring is R-configuration, and the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is cis;
In the formula (1), the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is the trans configuration, A compound in which the relative configuration of the double bond present in the substituent at the 3-position of the propane ring is the Z configuration;
In the formula (1), the absolute configuration at the 1-position of the cyclopropane ring is an R configuration, the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a cis configuration, A compound in which the relative configuration of the double bond present in the substituent at the 3-position of the propane ring is the Z configuration;
In formula (1), the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, and the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is rich in trans. Compound;
In the formula (1), the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, and the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is trans. % Or more compounds;
In the formula (1), the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, and the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is trans. % Or more compounds;

In the formula (1), a compound wherein the absolute configuration at the 1-position of the cyclopentenolone ring is the S configuration;
In the formula (1), a compound in which the absolute configuration at the 1-position of the cyclopentenolone ring is the S configuration and the absolute configuration at the 1-position of the cyclopropane ring is the R configuration;
In the formula (1), a compound in which the absolute configuration at the 1-position of the cyclopentenolone ring is the S configuration and the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a trans configuration ;
In the formula (1), a compound in which the absolute configuration at the 1-position of the cyclopentenolone ring is the S configuration and the relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a cis configuration ;
In the formula (1), a compound in which the absolute configuration at the 1-position of the cyclopentenolone ring is the S-configuration and the relative configuration of the double bond present in the substituent at the 3-position of the cyclopropane ring is the Z-configuration;
In the formula (1), the absolute configuration at the 1-position of the cyclopentenolone ring is the S configuration, the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, the substituent at the 1-position of the cyclopropane ring and the cyclopropane ring 3 A compound in which the relative configuration with the substituent at the position is trans;
In the formula (1), the absolute configuration at the 1-position of the cyclopentenolone ring is the S configuration, the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, the substituent at the 1-position of the cyclopropane ring and the cyclopropane ring 3 A compound whose relative configuration with the substituent at the position is cis;
In the formula (1), the absolute configuration at the 1-position of the cyclopentenolone ring is the S configuration, the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, the substituent at the 1-position of the cyclopropane ring and the cyclopropane ring 3 A compound in which the relative configuration with the substituent at the position is the trans configuration, and the relative configuration of the double bond present in the substituent at the 3-position of the cyclopropane ring is the Z configuration;
In the formula (1), the absolute configuration at the 1-position of the cyclopentenolone ring is the S configuration, the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, the substituent at the 1-position of the cyclopropane ring and the cyclopropane ring 3 A compound in which the relative configuration with the substituent at the position is cis configuration, and the relative configuration of the double bond existing in the substituent at the 3-position of the cyclopropane ring is Z configuration;
In the formula (1), the absolute configuration at the 1-position of the cyclopentenolone ring is the S configuration, the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, the substituent at the 1-position of the cyclopropane ring and the cyclopropane ring 3 Compounds rich in those whose relative configuration with the substituent at the position is trans;
In the formula (1), the absolute configuration at the 1-position of the cyclopentenolone ring is the S configuration, the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, the substituent at the 1-position of the cyclopropane ring and the cyclopropane ring 3 Compounds whose relative configuration with the substituent at the position is trans is 80% or more;
In the formula (1), the absolute configuration at the 1-position of the cyclopentenolone ring is the S configuration, the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, the substituent at the 1-position of the cyclopropane ring and the cyclopropane ring 3 A compound in which the relative configuration with the substituent at the position is 90% or more is trans. ;

で示されるアルコール化合物と、式（３）

で示されるカルボン酸化合物又はその反応性誘導体（例えば、酸ハロゲン化物、酸無水物等）とを反応させる方法。
該反応は、通常、縮合剤又は塩基の存在下、溶媒中で行なわれる。
縮合剤としては、例えば、ジシクロヘキシルカルボジイミド及び１−（３−ジメチルアミノプロピル）−３−エチルカルボジイミド ハイドロクロライドが挙げられる。
塩基としては、トリエチルアミン、ピリジン、Ｎ，Ｎ−ジエチルアニリン、４−ジメチルアミノピリジン、ジイソプロピルエチルアミン等の有機塩基が挙げられる。
溶媒としては、例えばベンゼン、トルエン及びヘキサン等の炭化水素、ジエチルエ−テル及びテトラヒドロフラン等のエ−テル、並びに、ジクロロメタン、１，２−ジクロロエタン及びクロロベンゼン等のハロゲン化炭化水素、及びこれらの混合溶媒等が挙げられる。
反応時間は、通常、５分間〜７２時間の範囲である。
反応温度は、通常、−２０℃〜１００℃（但し、使用する溶媒の沸点が１００℃未満の場合には、−２０℃〜溶媒の沸点）の範囲であり、好ましくは−５℃〜１００℃（但し、使用する溶媒の沸点が１００℃未満の場合には、−５℃〜溶媒の沸点）の範囲である。
該反応において、式（２）で示されるアルコ−ルと、式（３）で示されるカルボン酸化合物又はその反応性誘導体の使用モル比は任意に設定できるが、等モル又はそれに近い比で行なうのが好ましい。
縮合剤又は塩基は、式（２）で示されるアルコ−ル１モルに対して、通常は０．２５モルから過剰量まで任意の割合で使用することができ、好ましくは０．５モル〜５モルである。これらの縮合剤又は塩基は、式（３）で示されるカルボン酸化合物又はその反応性誘導体（式（３）で示されるカルボン酸化合物の例えば、対応する酸クロライド、酸ブロマイド、酸無水物等）の種類により適宜選択される。
反応終了後の反応混合物は、これを濾過して濾液を濃縮する、又は、これを水に注加した後に有機溶媒抽出、濃縮する等の通常の後処理操作を施すことにより、本発明化合物を得ることができる。得られた本発明化合物はクロマトグラフィ−、蒸留等の操作によって精製することができる。 The compound of the present invention can be produced, for example, by the method shown below.
Formula (2)

An alcohol compound represented by formula (3)

Or a reactive derivative thereof (for example, acid halide, acid anhydride, etc.).
The reaction is usually performed in a solvent in the presence of a condensing agent or a base.
Examples of the condensing agent include dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
Examples of the base include organic bases such as triethylamine, pyridine, N, N-diethylaniline, 4-dimethylaminopyridine, diisopropylethylamine.
Examples of the solvent include hydrocarbons such as benzene, toluene and hexane, ethers such as diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chlorobenzene, and mixed solvents thereof. Is mentioned.
The reaction time is usually in the range of 5 minutes to 72 hours.
The reaction temperature is usually in the range of −20 ° C. to 100 ° C. (however, when the boiling point of the solvent used is less than 100 ° C., it is −20 ° C. to the boiling point of the solvent), preferably −5 ° C. to 100 ° C. (However, when the boiling point of the solvent used is less than 100 ° C., the range is −5 ° C. to the boiling point of the solvent).
In the reaction, the molar ratio of the alcohol represented by the formula (2) and the carboxylic acid compound represented by the formula (3) or a reactive derivative thereof can be set arbitrarily, but the molar ratio is equal to or close to that. Is preferred.
The condensing agent or base can be used in an arbitrary ratio from 0.25 mol to an excess amount with respect to 1 mol of the alcohol represented by the formula (2), preferably 0.5 to 5 mol. Is a mole. These condensing agents or bases are carboxylic acid compounds represented by the formula (3) or reactive derivatives thereof (for example, the corresponding acid chlorides, acid bromides, acid anhydrides, etc. of the carboxylic acid compounds represented by the formula (3)). It is appropriately selected depending on the type.
The reaction mixture after completion of the reaction is filtered to concentrate the filtrate, or poured into water and then subjected to usual post-treatment operations such as organic solvent extraction and concentration, whereby the compound of the present invention is obtained. Obtainable. The obtained compound of the present invention can be purified by operations such as chromatography and distillation.

  A commercial item can be used for the alcohol compound shown by Formula (2). The carboxylic acid compound represented by the formula (3) is a compound described in, for example, Agricultural & Biological Chemistry, 34, p.1119 (1970), and can be produced by the method described in the literature.

Examples of pests for which the compounds of the present invention are effective include harmful arthropods such as harmful insects and harmful mites, and specific examples thereof include the following.
Lepidopterous insect pests: Japanese moths such as Nikaamega, Konoumeiga, Noshimekokuga, Japanese cypresses, Ayayoto, Yotoga, etc. Agrotis spp., Helicoverpa spp., Heliothis spp., Culex, Ichimongiseseri, Iga, Koiga, etc. Aedes such as Aedes aegypti, Aedes albopictus, Anopheles such as Sycaenidae, Aedes, Housefly, Housefly, Housefly, Housefly, etc. Drosophila, butterflies, fleas, aphids, flyfish, sand flies, dolphins, etc. Reticulate pests: German cockroaches, black cockroaches, American cockroaches, giant cockroaches, winged cockroaches, etc .: Ants, hornets, Locust pests such as wasps and wasps, etc .: Pests such as dog fleas, cat fleas, fleas, etc. Leafhoppers such as white-footed planthoppers, leafhoppers such as leafhoppers and leafhoppers, aphids, stink bugs, whiteflies, scale insects, bedbugs, etc. Corn rootworms such as worms, Japanese corn rootworms, western corn rootworms, southern corn rootworms, scarabs such as Douganebububui, himekogane, weevil such as weevil, weevil, weevil such as weevil, azuki beetle Hornworms, rice beetles, beetle horn beetles, potato beetles, etc. Pests: Southern Thrips thrips, Citrus thrips, Hana thrips, etc. Straight pests: Kella, grasshoppers and other ticks: Leopards, such as the leopard mites Mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites , Ticks such as spider mites, wing mites such as winged ticks, spiders.

The pest control agent of the present invention may be the compound of the present invention itself, but is usually used as the following preparation. Examples of the preparation include oils, emulsions, wettable powders, flowables (suspensions in water, emulsions in water, etc.), microcapsules, powders, granules, tablets, aerosols, carbon dioxide preparations, and heat evaporation agents. (Insecticide incense sticks, electric insecticide mats, liquid-absorbing core-type heat-pewing insecticides, etc.), piezo-type insecticides, heated smoke smoke (self-burning smoke smoke, chemical reaction smoke smoke, porous ceramic plate smoke smoke, etc.) ), Non-heated transpiration agent (resin transpiration agent, paper transpiration agent, non-woven fabric transpiration agent, knitted fabric transpiration agent, sublimation tablet, etc.), fumes (hooking etc.), direct contact agent (sheet contact agent, tape contact) Agents, net contact agents, etc.), ULV agents and poison baits.

Examples of the formulation method include the following methods.
(1) A method in which the compound of the present invention is mixed with a solid carrier, liquid carrier, gaseous carrier, bait and the like, and a surfactant and other formulation adjuvants are added and processed as necessary.
(2) A method of impregnating a base material containing no active ingredient with the compound of the present invention.
(3) A method of molding after mixing the compound of the present invention and the substrate.
These preparations usually contain 0.001 to 98% by weight of the compound of the present invention, depending on the form of preparation.

Examples of solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, bentonite, fusami clay, acidic clay), synthetic hydrous silicon oxide, talc, ceramics, and other inorganic minerals (sericite, quartz, sulfur). , Activated carbon, calcium carbonate, hydrated silica, etc.), fine powders and particulates such as chemical fertilizers (ammonium sulfate, phosphorous acid, ammonium nitrate, ammonium chloride, urea, etc.), solid substances at room temperature (2,4,6-triisopropyl) -1,3,5-trioxane, naphthalene, p-dichlorobenzene, camphor, adamantane, etc.), wool, silk, cotton, hemp, pulp, synthetic resin (for example, low density polyethylene, linear low density polyethylene, high Polyethylene resin such as density polyethylene; ethylene-vinyl ester copolymer such as ethylene-vinyl acetate copolymer; ethylene-methyl methacrylate copolymer , Ethylene-methacrylic acid ester copolymer such as ethylene-ethyl methacrylate copolymer; ethylene-acrylic acid ester copolymer such as ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer; ethylene -Ethylene-vinyl carboxylic acid copolymer such as acrylic acid copolymer; ethylene-tetracyclododecene copolymer; polypropylene resin such as propylene homopolymer, propylene-ethylene copolymer; poly-4-methylpentene -1, polybutene-1, polybutadiene, polystyrene; acrylonitrile-styrene resin; styrene-based elastomers such as acrylonitrile-butadiene-styrene resin, styrene-conjugated diene block copolymer, hydrogenated styrene-conjugated diene block copolymer; fluorine Resin; Polymeta Acrylic resins such as methyl acrylate; Polyamide resins such as nylon 6 and nylon 66; Polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polycyclohexylene dimethylene terephthalate; Polycarbonate, polyacetal, poly Acrylic sulfone, polyarylate, hydroxybenzoic acid polyester, polyetherimide, polyester carbonate, polyphenylene ether resin, polyvinyl chloride, polyvinylidene chloride, polyurethane, foamed polyurethane, foamed polypropylene, foamed ethylene and other porous resins), glass, Felts, fibers, fabrics, knitted fabrics, sheets, paper, threads, foams, porous bodies and multifilaments made of one or more of metals, ceramics, etc. I can get lost.

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

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

Surfactants include, for example, alkyl sulfate esters, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers, polyarylethylenes of alkyl aryl ethers, polyethylene glycol ethers, polyhydric alcohol esters and sugars. Examples include alcohol derivatives.

Other formulation adjuvants include fixing agents, dispersants and stabilizers, such as casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, saccharides, Synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone), polyacrylic acid, etc., BHT (2,6-di-tert-butyl-4-methylphenol), and BHA (2-tert-butyl-4-methoxyphenol) 3-tert-butyl-4-methoxyphenol).

Examples of the insecticidal incense base material include a mixture of a vegetable powder such as wood powder and straw powder and a binder such as tab powder, starch and gluten.
Examples of the base material for the insecticidal electric mat include those obtained by solidifying a cotton linter into a plate shape and those obtained by solidifying a fillable of a mixture of cotton linter and pulp into a plate shape.
Examples of the base material of the self-combustion type smoke agent include nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethyl cellulose, wood powder and other combustion exothermic agents, alkali metal salts, alkaline earth metal salts, heavy metals. Examples thereof include pyrolysis stimulants such as chromate and chromate, oxygen supply agents such as potassium nitrate, flame retardants such as melamine and wheat starch, extenders such as diatomaceous earth, and binders such as synthetic glue.

Examples of the base material for the chemical reaction type smoke agent include exothermic agents such as alkali metal sulfides, polysulfides, hydrosulfides, and calcium oxide, catalyst materials such as carbonaceous materials, iron carbide, and activated clay, azo Examples thereof include organic foaming agents such as dicarbonamide, benzenesulfonyl hydrazide, dinitropentamethylenetetramine, polystyrene and polyurethane, and fillers such as natural fiber pieces and synthetic fiber pieces.

Examples of the resin used for the substrate such as a resin transpiration agent include polyethylene resins such as low density polyethylene, linear low density polyethylene, and high density polyethylene; and ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer. Polymer; ethylene-methacrylic acid ester copolymer such as ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer; ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, etc. Ethylene-acrylic acid ester copolymer; ethylene-vinyl carboxylic acid copolymer such as ethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymer; propylene copolymer, propylene-ethylene copolymer, etc. Polypropylene resin; poly-4-methylpentene-1, polybutene-1, poly Styrenic elastomers such as butadiene, polystyrene, acrylonitrile-styrene resins; acrylonitrile-butadiene-styrene resins, styrene-conjugated diene copolymers, styrene-conjugated diene block copolymers, hydrogenated products; fluororesins; polymethyl methacrylate, etc. Acrylic acid resin; Polyamide resin such as nylon 6 and nylon 66; Polyester resin such as polyethylene terephthalate, polyethylene naphthalate, polybutylene butarate, polycyclohexylene dimethylene terephthalate; Polycarbonate, polyacetal, polyacrylsulfone, polyarylate , Hydroxybenzoic acid polyester, Polyetherimide, Polyester carbonate, Polyphenylene ether resin, Polyvinyl chloride, Polyvinyl chloride These base materials may be used alone or as a mixture of two or more. These base materials may contain phthalates (dimethyl phthalate, dioctyl phthalate, etc.) as necessary. Further, a plasticizer such as adipic acid esters and stearic acid may be added. The resin transpiration agent can be obtained by kneading the compound of the present invention in the above-mentioned base material and then molding it by injection molding, extrusion molding, press molding or the like. The obtained resin preparation can be processed into a plate shape, a film shape, a tape shape, a net shape, a string shape or the like through steps such as molding and cutting if necessary. These resin preparations are processed, for example, as animal collars, animal ear tags, sheet preparations, attracting strings, or gardening supports.

Examples of poison bait base materials include bait ingredients such as cereal flour, vegetable oil, sugar, crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, and pepper powder. Anti-fouling agents for children and pets, and pest-attracting perfumes such as cheese flavor, onion flavor, peanut oil and the like.

The pest control method of the present invention is carried out by applying an effective amount of the compound of the present invention to a pest or a pest habitat, usually in the form of the pest control agent of the present invention.
Examples of the method for applying the pest control agent of the present invention include the following methods, which can be appropriately selected depending on the form, place of use, etc. of the pest control agent of the present invention.
(1) A method of treating the pest control agent of the present invention as it is in a pest or a habitat of the pest.
(2) A method in which the pest control agent of the present invention is diluted with a solvent such as water and then sprayed to a pest or a habitat of the pest.
In this case, the pest control agent of the present invention formulated in an emulsion, wettable powder, flowable agent, microcapsule preparation or the like is usually diluted so that the concentration of the compound of the present invention becomes 0.1 to 10,000 ppm. .
(3) A method in which the pest control agent of the present invention is heated in a pest habitat to volatilize active ingredients.
In this case, both the application amount and the application concentration of the compound of the present invention can be appropriately determined according to the form of the pest control agent of the present invention, the application time, the application place, the application method, the type of the pest, the damage situation, etc. .

When the compound of the present invention is used for prevention of epidemics, the application rate is usually 0.0001 to 1000 mg / m ³ as the amount of the compound of the present invention when applied to space, and 0.0001 to 1000 when applied to a plane. 1000 mg / m ² . Insecticidal incense sticks, electric insecticidal mats, and the like are applied by volatilizing active ingredients by heating in accordance with the formulation form. Resin transpiration agents, paper transpiration agents, non-woven fabric transpiration agents, knitted fabric transpiration agents, sublimable tablets and the like can be used, for example, by leaving them in the space to be applied as they are and by placing them in the preparation under ventilation.
Examples of the space to which the pest control composition of the present invention is applied for epidemics include closets, closets, Japanese dance, cupboards, toilets, bathhouses, storerooms, living rooms, canteens, warehouses, car interiors, and the like. It can also be applied in open spaces.

When the pest control composition of the present invention is used for controlling ectoparasites of domestic animals such as cattle, horses, pigs, sheep, goats and chickens, and small animals such as dogs, cats, rats and mice, it is well known in veterinary medicine. Can be used on animals in any way. As a specific method of use, when systemic control is intended, for example, it is administered by tablet, feed mixing, suppository, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.) For purposes of non-systemic control, for example, spraying oils or aqueous solutions, pour-on or spot-on treatment, washing animals with shampoo formulations or It is used by a method such as attaching a resin transpiration agent to an animal using a collar or ear tag. The amount of the compound of the present invention when administered to an animal body is usually in the range of 0.01 to 1000 mg per 1 kg body weight of the animal.

The compound of the present invention is used in combination with or in combination with other insecticides, acaricides, nematicides, soil pest control agents, fungicides, herbicides, plant growth regulators, repellents, synergists, fertilizers, soil conditioners. It can also be used.

Examples of the active ingredients of such insecticides and acaricides include fenitrothion, fenthion, diazinon, chlorpyrifos, acephate, metidathion, disulfotone, DDVP, sulfophos, cyanophos, dioxabenzophos, dimethoate, phentoate, malathion, trichlorfone, azinephosmethyl, Organophosphorus compounds such as monocrotophos and ethion;
Carbamate compounds such as BPMC, benfuracarb, propoxyl, carbosulfurphan, carbaryl, mesomil, etiophencarb, aldicarb, oxamyl, phenothiocarb;
Etofenprox, fenvalerate, esfenvalerate, fenpropatoline, cypermethrin, permethrin, cyhalothrin, deltamethrin, cycloprotorin, fulvalinate, bifenthrin, 2-methyl-2- (4-bromodifluoromethoxyphenyl) propyl (3 -Phenoxybenzyl) ether, tralomethrin, silafluophene, d-phenothrin, ciphenothrin, d-resmethrin, acrinathrin, cyfluthrin, tefluthrin, transfluthrin, tetramethrin, allethrin, d-flamethrin, praretrin, imiprotorin, 5-pentrin 2-propynyl) furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate, metofluthrin, profluthrin, dimethyl Pyrethroid compounds such as trin;
Nitroimidazolidine derivatives, nitroguanidine derivatives such as clothianidin and dinotefuran, N-cyanoamidine derivatives such as acetamiprid, endosulfan, γ-BHC, chlorinated hydrocarbons such as 1,1-bis (chlorophenyl) -2,2,2-trichloroethanol Compound, benzoylphenylurea compounds such as chlorfluazuron, teflubenzuron, flufenoxuron, phenylpyrazole compounds, methoxadiazone, bromopropyrate, tetradiphone, quinomethionate, pyridaben, fenpyroximate, diafenthiuron, tebufenpyrad, polynactin complex [Tetranactin, dinactin, trinactin], pyrimidifen, milbemectin, abamectin, ivermectin, and azadirachtin It is below.

As an active ingredient of a repellent, for example, 3,4-caranediol, N, N-diethyl-m-toluamide, 1-methylpropyl 2- (2-hydroxyethyl) -1-piperidinecarboxylate, p-menthane-3 , 8-diol, and plant essential oils such as hyssop oil.

As an active ingredient of a synergist, for example, bis- (2,3,3,3-tetrachloropropyl) ether (S-421), N- (2-ethylhexyl) bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide (MGK-264), and Α- [2- (2-butoxyethoxy) ethoxy] -4,5-methylenedioxy-2-propyltoluene (piperonylbutoxide).

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

（１Ｓ）−２−メチル−４−オキソ−３−（２−プロピニル）−２−シクロペンテニル＝（１Ｒ）−トランス−３−（（Ｚ）−２−シアノ−１−プロペニル）−２，２−ジメチルシクロプロパンカルボキシレート（以下、本発明化合物（１）と記す。）２５７ｍｇを黄色結晶として得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．２２（ｓ，３Ｈ）、１．３３（ｓ，３Ｈ）、１．７４（ｄ，１Ｈ，J ＝ ５．１ Ｈｚ）、１．９７（ｄ，３Ｈ，J ＝ １．４ Ｈｚ）、１．９９（ｔ，１Ｈ，J ＝ ２．９ Ｈｚ）、２．１８（ｓ,３Ｈ）、２．２６（ｄｄ，１Ｈ，J ＝ １８．７，２．９ Ｈｚ）、２．４７（ｄｄ，１Ｈ，J ＝ ９．５，５．１ Ｈｚ）、２．９１（ｄｄ，１Ｈ，Ｊ＝１８．７，６．３ Ｈｚ）、３．１６（ｓ、２Ｈ）、５．７１（ｄ，１Ｈ，J ＝ ６．３ Ｈｚ）、５．８４（ｄｄ，１Ｈ，J ＝ ９．４，１．４ Ｈｚ） First, the manufacture example of this invention compound is shown.
Production Example 1
(4S) -Hydroxy-3-methyl-2- (2-propynyl) -2-cyclopentenone (251 mg, 1.67 mmol), (1R) -trans-3-((Z) -2-cyano-1- To a chloroform solution (15 mL) of propenyl) -2,2-dimethylcyclopropanecarboxylic acid (200 mg, 1.15 mmol), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (320 mg, 1.67 mol), 4-Dimethylaminopyridine (5 mg) was added. After stirring at room temperature for 18 hours, water was poured into the reaction solution, which was extracted with ethyl acetate. The organic layer is dried over magnesium sulfate and then concentrated under reduced pressure. The residue is subjected to silica gel column chromatography and is represented by the following formula.

(1S) -2-Methyl-4-oxo-3- (2-propynyl) -2-cyclopentenyl = (1R) -trans-3-((Z) -2-cyano-1-propenyl) -2,2 -257 mg of dimethylcyclopropanecarboxylate (hereinafter referred to as the present compound (1)) was obtained as yellow crystals.
¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.22 (s, 3H), 1.33 (s, 3H), 1.74 (d, 1H, J = 5.1 Hz), 1 .97 (d, 3H, J = 1.4 Hz), 1.99 (t, 1H, J = 2.9 Hz), 2.18 (s, 3H), 2.26 (dd, 1H, J = 18.7, 2.9 Hz), 2.47 (dd, 1H, J = 9.5, 5.1 Hz), 2.91 (dd, 1H, J = 18.7, 6.3 Hz), 3.16 (s, 2H), 5.71 (d, 1H, J = 6.3 Hz), 5.84 (dd, 1H, J = 9.4, 1.4 Hz)

Next, formulation examples are shown. In addition, a part shows a mass part.
Formulation Example 1
Dissolve 20 parts of the compound of the present invention in 65 parts of xylene, add 15 parts of Solpol 3005X (Toho Chemical Registration) and stir well to obtain an emulsion.

Formulation Example 2
Add 5 parts of Solpol 3005X to 40 parts of the present compound, mix well, add 32 parts of Carplex # 80 (Synthetic Hydrous Hydrous, Shionogi Pharmaceutical) and 23 parts of 300 mesh diatomaceous earth, and stir and mix with a juice mixer. To obtain a wettable powder.

Formulation Example 3
1.5 parts of the compound of the present invention, 1 part of Toxeal GUN (synthetic hydrous oxide, manufactured by Tokuyama Corporation), 1 part, LAX 85A (sodium lignin sulfonate, manufactured by West vaco chemicals), 2 parts, bentonite Fuji (made by bentonite, Hojun Co.) 30 parts and 65.5 parts of Katsumiyama A clay (Kaolin clay, manufactured by Katsumiyama Mining Co., Ltd.) are thoroughly pulverized and mixed, mixed well with water, granulated with an extrusion granulator, and dried. 1.5% granules are obtained.

Formulation Example 4
After mixing 10 parts of the present compound, 10 parts phenylxylylethane and 0.5 parts Sumidur L-75 (tolylene diisocyanate, manufactured by Sumitomo Bayer Urethane Co., Ltd.), the mixture was added to 20 parts of a 10% aqueous solution of gum arabic. Stir with a homomixer to obtain an emulsion with an average particle size of 20 μm. 2 parts of ethylene glycol is added thereto, and further stirred for 24 hours in a warm bath at 60 ° C. to obtain a microcapsule slurry. On the other hand, 0.2 parts of xanthan gum and 1.0 part of bee gum R (aluminum magnesium silicate, manufactured by Sanyo Kasei) are dispersed in 56.3 parts of ion-exchanged water to obtain a thickener solution. 42.5 parts of the microcapsule slurry and 57.5 parts of the thickener solution are mixed to obtain a microcapsule.

Formulation Example 5
After mixing 10 parts of the compound of the present invention and 10 parts of phenylxylylethane, it is added to 20 parts of a 10% aqueous solution of polyethylene glycol and stirred with a homomixer to obtain an emulsion having an average particle size of 3 μm. On the other hand, 0.2 parts of xanthan gum and 1.0 part of bee gum R (aluminum magnesium silicate, manufactured by Sanyo Chemical) are dispersed in 58.8 parts of ion-exchanged water to obtain a thickener solution. 40 parts of the emulsion solution and 60 parts of the thickener solution are mixed to obtain a flowable agent.

Formulation Example 6
5 parts of the compound of the present invention is 3 parts of Carplex # 80 (synthetic hydrous hydrous powder, Shionogi Pharmaceutical registered trademark), PAP (mixture of monoisopropyl phosphate and diisopropyl phosphate) 0.3 part and talc (300 mesh) 91 Add 7 parts and stir and mix with a juice mixer to obtain a powder.

Formulation Example 7
0.1 part of the compound of the present invention is dissolved in 10 parts of dichloromethane, and this is mixed with 89.9 parts of deodorized kerosene to obtain an oil.

Formulation Example 8
1 part of the compound of the present invention, 5 parts of dichloromethane and 34 parts of deodorized kerosene are mixed and dissolved, filled into an aerosol container, and after attaching the valve part, 60 parts of propellant (liquefied petroleum gas) is pressurized and charged through the valve part. To obtain an oily aerosol.

Formulation Example 9
An aerosol container is filled with 0.6 parts 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 Co., Ltd.) and 50 parts of water. 40 parts of propellant (liquefied petroleum gas) is pressurized and filled through the valve portion to obtain an aqueous aerosol.

Formulation Example 10
0.3 g of the compound of the present invention is dissolved in 20 ml of acetone, and 99.7 g of the incense base material (mixed in a ratio of tab powder: straw powder: wood powder = 4: 3: 3) is stirred and mixed uniformly. After that, 100 ml of water is added, and the kneaded mixture is molded and dried to obtain an insecticidal incense.

Formulation Example 11
Acetone is added to 0.8 g of the compound of the present invention and 0.4 g of piperonyl butoxide and dissolved to make a total of 10 ml. 0.5 ml of this solution is impregnated uniformly into a 2.5 cm × 1.5 cm, 0.3 cm thick electric insecticidal mat substrate (a mixture of cotton linter and pulp mixed in a plate shape) Get an electric insecticidal matting agent.

Formulation Example 12
Liquid core obtained by dissolving 3 parts of the compound of the present invention in 97 parts of deodorized kerosene into a vinyl chloride container and heated at the top with a heater (inorganic powder solidified with binder and sintered) ) Is inserted to obtain parts for use in the liquid absorption core type heat transpiration apparatus.

Formulation Example 13
100 mg of the compound of the present invention is dissolved in an appropriate amount of acetone and impregnated into a porous ceramic plate having a size of 4.0 cm × 4.0 cm and a thickness of 1.2 cm to obtain a heated smoke agent.

Formulation Example 14
100 μg of the compound of the present invention is dissolved in an appropriate amount of acetone, and uniformly applied to a filter paper having a size of 2 cm × 2 cm and a thickness of 0.3 mm, and then acetone is air-dried to obtain a room temperature volatilizer.

で示される（１Ｓ）−３−アリルー２−メチル−4−オキソ−２−シクロペンテニル＝（１Ｒ）−トランス−３−（（Ｚ）-２−シアノ−１−プロペニル）−２，２−ジメチルシクロプロパンカルボキシレート（特公昭３９−４０７４公報に記載の化合物。以下、比較化合物（１）と記す。）、および下記式

で示される（１Ｓ）−２−メチル−4−オキソ−３−（２−プロピニル）−２−シクロペンテニル＝（１Ｒ）−トランス−３−（２−メチル−１−プロペニル）−２，２−ジメチルシクロプロパンカルボキシレート（特開平０３−２０６００８号公報に記載の化合物。以下、比較化合物（２）と記す。）を用いて同様に試験を行った。ノックダウン率は下式により計算した。
ノックダウン率（％）＝（ノックダウン虫数／供試虫数）×１００
２分後の結果を表１に示す。 Next, it shows as a test example that this invention compound is effective as an active ingredient of a pest control agent.
Test example 1
This invention compound (1) 0.1 part manufactured in the said manufacture example was melt | dissolved in 10 parts of dichloromethane, this was mixed with 89.9 parts of deodorizing kerosene, and 0.1% oil agent was prepared.
Six American cockroaches (3 males and 2 females) are placed in a test container with a buttered inner wall (diameter 12.5 cm, height 10 cm, bottom 16 mesh wire mesh) and the container is placed in a test chamber ( (Bottom: 46 cm × 46 cm, height: 70 cm). From the height of 60 cm above the upper surface of the container, 1.5 ml of the oil of the compound (1) of the present invention was sprayed using a spray gun (spray pressure 0.4 kg / cm ² ). The container was removed from the test chamber 30 seconds after spraying, the number of insects knocked down after a certain time was counted, and the knockdown rate was determined (2 repeated averages).
In addition, the following formula as a control

(1S) -3-allyl-2-methyl-4-oxo-2-cyclopentenyl = (1R) -trans-3-((Z) -2-cyano-1-propenyl) -2,2-dimethyl Cyclopropanecarboxylate (compound described in JP-B-39-4074, hereinafter referred to as comparative compound (1)), and the following formula

(1S) -2-methyl-4-oxo-3- (2-propynyl) -2-cyclopentenyl = (1R) -trans-3- (2-methyl-1-propenyl) -2,2- Tests were similarly conducted using dimethylcyclopropanecarboxylate (a compound described in JP-A No. 03-206008, hereinafter referred to as Comparative Compound (2)). The knockdown rate was calculated by the following formula.
Knockdown rate (%) = (number of knockdown insects / number of test insects) × 100
The results after 2 minutes are shown in Table 1.

  The compound of the present invention showed an excellent knockdown effect against cockroaches.

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

Claims (3)

Formula (1)

A cyclopropanecarboxylic acid ester represented by A pest control agent comprising a cyclopropanecarboxylic acid ester represented by the formula (1) as an active ingredient. A method for controlling pests, wherein an effective amount of the cyclopropanecarboxylic acid ester represented by the formula (1) is applied to pests or habitats of pests.