JP2010024212A - 2-cyano-2,3,3-trimethylcyclopropanecarboxylic acid ester and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound having an excellent control effect on pests. <P>SOLUTION: A cyclopropanecarboxylic acid ester is represented by formula (1) (wherein R is a hydrogen atom, a fluorine atom, a 1-4C alkyl group, a 2-4C alkenyl group, a 2-4C alkynyl group, a 1-4C alkyloxy group, a 1-4C alkyloxymethyl group or a 1-4C alkylthiomethyl group). The pest controller comprises the cyclopropanecarboxylic acid ester represented by the formula (1) as an active ingredient. The method for controlling pests comprises applying an effective amount of the cyclopropanecarboxylic acid ester represented by the formula (1) to pests or pest habitats. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to 2-cyano-2,3,3-trimethylcyclopropanecarboxylic acid ester and use thereof.

  Conventionally, various compounds have been synthesized to control pests. For example, Patent Document 1 describes certain types of cyclopropanecarboxylic acid esters. However, the cyclopropanecarboxylic acid ester may not have sufficient pest control effect depending on the usage scene.

JP-A-57-165343

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

〔式中、
Ｒは水素原子、フッ素原子、Ｃ１〜Ｃ４アルキル基、Ｃ２〜Ｃ４アルケニル基、Ｃ２〜Ｃ４アルキニル基、Ｃ１〜Ｃ４アルキルオキシ基、Ｃ１〜Ｃ４アルキルオキシメチル基またはＣ１〜Ｃ４アルキルチオメチル基を表す。〕
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；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；および、本発明化合物の製造中間体を提供する。 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)
Formula (1)

[Where,
R 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 alkyloxy group, a C1-C4 alkyloxymethyl group, or a C1-C4 alkylthiomethyl group. ]
A pesticide containing the compound of the present invention as an active ingredient; an effective amount of the compound of the present invention as a pest or pest A method for controlling pests characterized by being applied to a habitat of the present invention; and a production intermediate of the compound of the present invention.

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

  The compound of the present invention has two asymmetric carbon atoms at the 1-position and the 3-position on the cyclopropane ring. In the compound of the present invention, the configuration at the 1-position is the S configuration, and the configuration at the 3-position is S configuration, the relative configuration of the 1-position substituent and the 3-position substituent in the cyclopropane ring is cis; that is, (1S) cis-cyclopropanecarboxylic acid ester.

In the substituent represented by R,
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 alkenyl group include an ethynyl group and a 2-propynyl group.
Examples of the C1-C4 alkyloxy group include a methoxy group, an ethoxy group, and a propoxy group.
Examples of the C1-C4 alkyloxymethyl group include a methoxymethyl group, an ethoxymethyl group, and a propoxymethyl group.
Examples of the C1-C4 alkylthiomethyl group include a methylthiomethyl group, an ethylthiomethyl group, and a propylthiomethyl group.

で示されるアルコールと、式（３）

で示されるカルボン酸とを反応させることにより製造することができる。 The compound of the present invention has the formula (2)

An alcohol represented by formula (3)

It can manufacture by making it react with carboxylic acid shown by these.

〔式中、Ｒは前記と同じ意味を表す。〕
との混合物を得ることができる。該混合物をクロマトグラフィー等の分離操作に付すことにより、本発明化合物を単離することができる。必要であれば、単離された本発明化合物を蒸留等の精製操作に付して精製することもできる。 The reaction between the alcohol represented by the formula (2) and the carboxylic acid represented by the formula (3) will be described.
The reaction is usually performed in the presence of an acid catalyst or a condensing agent and further in the presence of a solvent.
As a solvent used in the reaction, a solvent inert in the reaction can be used. Specifically, for example, hydrocarbons such as toluene and hexane, ethers such as diethyl ether and tetrahydrofuran, chloroform, dichloromethane, 1,2-dichloroethane. And halogenated hydrocarbons such as these and mixed solvents thereof.
Examples of the acid catalyst used in the reaction include inorganic acids such as sulfuric acid, and sulfonic acids such as paratoluenesulfonic acid and methanesulfonic acid. When an acid catalyst is used, the amount of the acid catalyst is usually in the range of 0.01 to 20 mol with respect to 1 mol of the carboxylic acid represented by the formula (3), and can be appropriately changed depending on the reaction situation. it can.
Examples of the condensing agent used in the reaction include dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, and the like. When the condensing agent is used, the amount of the condensing agent is usually 1 mol with respect to 1 mol of the carboxylic acid represented by the formula (3), but can be appropriately changed according to the reaction situation.
The amount of the alcohol represented by the formula (2) is usually 1 mol with respect to 1 mol of the carboxylic acid represented by the formula (3), but can be appropriately changed depending on the reaction situation.
The reaction time is usually in the range of instantaneous to 72 hours, and the reaction temperature is usually in the range of -20 ° C to 100 ° C.
After completion of the reaction, the reaction mixture is poured into water, extracted with an organic solvent, and then subjected to ordinary post-treatment operations such as concentration, whereby the compound of the present invention and the formula (1 ′)

[Wherein, R represents the same meaning as described above. ]
A mixture with can be obtained. The compound of the present invention can be isolated by subjecting the mixture to a separation operation such as chromatography. If necessary, the isolated compound of the present invention can be purified by subjecting it to a purification operation such as distillation.

〔式中、Ｘはメトキシ、エトキシ、イソプロポキシ等の炭素数１〜５の低級アルコキシ基を表す。〕
で示されるカルボン酸エステルを得ることができる。
式（３ａ）で示されるカルボン酸エステルを、クロマトグラフィー等の分離操作に付すことにより、下記式（３ｂ）で示されるカルボン酸エステルを得ることができる。
式（３ｂ）で示されるカルボン酸エステルは、水存在下に酸触媒または塩基と反応させることにより、下記式（３ｃ）で示されるカルボン酸を得ることができる。

Further, the carboxylic acid represented by the formula (3) and a lower alcohol such as methanol, ethanol and isopropanol are treated in the same manner as in the above reaction in the presence of an acid catalyst or a condensing agent.

[Wherein, X represents a lower alkoxy group having 1 to 5 carbon atoms such as methoxy, ethoxy and isopropoxy. ]
Can be obtained.
The carboxylic acid ester represented by the following formula (3b) can be obtained by subjecting the carboxylic acid ester represented by the formula (3a) to a separation operation such as chromatography.
The carboxylic acid ester represented by the formula (3b) can be reacted with an acid catalyst or a base in the presence of water to obtain a carboxylic acid represented by the following formula (3c).

  This invention compound can also be manufactured by replacing with the carboxylic acid shown by Formula (3), and carrying out similarly to the reaction shown above using the carboxylic acid shown by Formula (3c).

で示される化合物と過ヨウ素酸塩とを、マンガンまたはルテニウムの酸化物の存在下に反応させることにより製造することができる。 The carboxylic acid represented by the formula (3) has the formula (7)

Can be produced by reacting a compound represented by the formula with periodate in the presence of an oxide of manganese or ruthenium.

The reaction is usually performed in the presence of a solvent.
Examples of the solvent used in the reaction include water or a mixed solvent composed of water and an organic solvent miscible with water. Examples of the organic solvent miscible with water include alcohol solvents such as tert-butyl alcohol, ketone solvents such as acetone and methyl ethyl ketone, nitrile solvents such as acetonitrile and propionitrile, N, N-dimethylformamide, N- Examples include amide solvents such as methyl pyrrolidone.
Examples of periodate used in the reaction include sodium metaperiodate and potassium metaperiodate.
Examples of the manganese oxide used in the reaction include sodium permanganate and potassium permanganate. Examples of the ruthenium oxide include ruthenium (IV) oxide anhydride and ruthenium (IV) oxide hydrate. Etc. Manganese oxides and ruthenium oxides prepared in the system may be used as they are.
The amount of manganese oxide or ruthenium oxide to be used is usually in the range of 0.1 to 1 mol with respect to 1 mol of the compound represented by formula (7), and the amount of periodate is represented by formula (7 ) Is usually in the range of 2 to 30 moles per mole of the compound shown.
The reaction time of the reaction is usually in the range of 12 to 96 hours, and the reaction temperature is usually in the range of 0 to 50 ° C.
After completion of the reaction, the carboxylic acid represented by the formula (3) can be isolated by performing a usual post-treatment operation such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating.

  The acid halide of the carboxylic acid represented by the formula (3), the acid anhydride of the carboxylic acid represented by the formula (3) or the lower alkyl ester of the carboxylic acid represented by the formula (3) are each represented by the formula (3): It can be produced by a known method using the carboxylic acid shown as a raw material.

  The alcohol compound represented by the formula (2) is a commercially available product, a compound described in JP-A No. 2000-63329, or the like, or can be produced according to the methods described in these documents.

The compound represented by the formula (7) can be produced, for example, by the method described in the following scheme.

Compound represented by formula (4) → compound represented by formula (5) In this reaction, the compound represented by formula (4) is reacted with a chlorinating agent (for example, oxalyl chloride), This is done by reacting.
The reaction is usually performed in a solvent. Examples of the solvent used for the reaction include ether solvents such as tetrahydrofuran.
The amount of the chlorinating agent used in the reaction is 1 mol of the theoretical amount with respect to 1 mol of the compound represented by the formula (4), but is usually in the range of 1 mol to large excess, preferably 1 mol to 3 mol. Can be selected as appropriate.
When the compound represented by the formula (4) is reacted with the chlorinating agent, it can be carried out in the presence of a base as necessary. Examples of the base that can be used include triethylamine, pyridine and the like. The reaction time for reacting the compound represented by formula (4) with the chlorinating agent is usually in the range of 1 to 24 hours, and the reaction temperature is usually in the range of 0 ° C to 50 ° C.
Subsequently, when making it react with ammonia, it is normally carried out by inject | pouring ammonia gas or ammonia water with respect to the reaction mixture or concentrate of the said process.
The amount of ammonia used in the reaction is 1 mol of the theoretical amount with respect to 1 mol of the compound represented by the formula (4), but is usually in the range of 1 mol to large excess, preferably 1 mol to 3 mol. It can be selected appropriately. The reaction time in the reaction with ammonia is usually in the range of 1 to 24 hours, and the reaction time is usually in the range of 0 ° C to 50 ° C.
After completion of the reaction, the compound represented by the formula (5) can be isolated by performing a usual post-treatment operation such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating.

-Compound shown by Formula (5)-> Compound shown by Formula (6) This reaction is performed by making the compound shown by Formula (5) react with acetic anhydride.
The amount of acetic anhydride used in the reaction is in the range of 5 mol to a large excess with respect to 1 mol of the compound represented by formula (5).
The reaction time is usually in the range of 1 to 24 hours, and the reaction time is usually in the range of 25 ° C. to the reflux temperature of acetic anhydride.
After completion of the reaction, the compound represented by the formula (6) can be isolated by performing a general post-treatment operation such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating. The isolated compound represented by the formula (6) can be purified by chromatography or the like.

Compound represented by formula (6) → compound represented by formula (7) The reaction is carried out by reacting the compound represented by formula (6) with methyl iodide in the presence of a base.
The reaction is usually performed in a solvent. Examples of the solvent used for the reaction include ether solvents such as tetrahydrofuran.
Examples of the base used in the reaction include organic lithium reagents such as n-butyllithium and sec-butyllithium. The amount of the base used in the reaction is in the range of 1 mol to 2 mol with respect to 1 mol of the compound represented by the formula (6). The amount of iodomethyl used in the reaction is in the range of 1 mol to 3 mol with respect to 1 mol of the compound represented by formula (6).
The reaction time of the reaction is usually in the range of 1 to 24 hours, and the reaction time is usually in the range of -78 ° C to 0 ° C.
After completion of the reaction, the compound represented by the formula (7) can be isolated by performing a usual post-treatment operation such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and concentrating the mixture. The isolated compound represented by the formula (7) can be purified by chromatography or the like.

  The compound represented by the formula (4) can be obtained by a production method according to the method described in, for example, JP-A-2001-278851.

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 glutin.
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 self-burning base materials include nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethyl cellulose, wood flour, and other combustion exothermic agents, alkali metal salts, alkaline earth metal salts, and dichromates. And pyrolysis stimulants such as chromate, oxygen supply agents such as potassium nitrate, flame retardants such as melamine and wheat starch, fillers such as diatomaceous earth, and binders such as synthetic pastes.

  Examples of the base material for the chemical reaction type smoke agent include exothermic agents such as alkali metal sulfides, polysulfides, hydrosulfides, and calcium oxide, catalyst 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 ester compound A and the ester compound B in the base material and then molding them 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 may be used in combination with or in combination with other insecticides, nematicides, soil pest control agents, fungicides, herbicides, plant growth regulators, repellents, synergists, fertilizers, soil improvers. You can also.

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 [alpha]-[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, test examples, and the like, but the present invention is not limited to these examples.

で示される４−メトキシメチル−２，３，５，６−テトラフルオロベンジル＝（１Ｓ）−シス−２−シアノ−２，３，３−トリ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）１４８ｍｇを得た。
無色結晶：¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．３０（ｓ，３Ｈ）、１．４５（ｓ，３Ｈ）、１．５６（ｓ，３Ｈ）、１．９６（ｓ，１Ｈ）、３．４１（ｓ，３Ｈ）、４．６０（ｓ，２Ｈ）、５．２５（ｓ，２Ｈ） First, the manufacture example of this invention compound is shown.
Production Example 1
Under nitrogen atmosphere, 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol 480 mg, (1S)-(trans / cis = 1/1) -2-cyano-2,3,3-trimethylcyclopropane To a mixture of 250 mg of carboxylic acid, 5 mg of 4-dimethylaminopyridine and 10 ml of chloroform, 470 mg of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide = hydrochloride was added and stirred at room temperature for 18 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and then concentrated under reduced pressure. To a 5 mL solution of the residue in anhydrous tetrahydrofuran was added 0.18 mL of triethylamine, 0.12 mL of acetic anhydride and 5 mg of 4-dimethylaminopyridine at room temperature, and the mixture was stirred at room temperature for 18 hours, and the remaining 4-methoxymethyl-2,3, 5,6-tetrafluorobenzyl alcohol was acetylated. Saturated aqueous sodium hydrogen carbonate was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer is dried over magnesium sulfate and concentrated. The resulting residue is subjected to silica gel column chromatography to obtain the following formula.

4-methoxymethyl-2,3,5,6-tetrafluorobenzyl = (1S) -cis-2-cyano-2,3,3-trimethylcyclopropanecarboxylate represented by the following formula (1) 148 mg was obtained.
Colorless crystals: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.30 (s, 3H), 1.45 (s, 3H), 1.56 (s, 3H), 1.96 (s , 1H), 3.41 (s, 3H), 4.60 (s, 2H), 5.25 (s, 2H)

で示される４−（２−プロピニル）−２，３，５，６−テトラフルオロベンジル＝（１Ｓ）−シス−２−シアノ−２，３，３−トリ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（２）と記す）を得た。
黄色液体：¹Ｈ−ＮＭＲ（ＣＤＣｌ₃，ＴＭＳ）δ（ｐｐｍ）：１．２７（ｓ，３Ｈ）、１．４９（ｓ，３Ｈ）、１．５０（ｓ，３Ｈ）、１．６２（ｓ，１Ｈ）、２．０７（ｔ，１Ｈ，J＝２．８Ｈｚ）、３．６５（ｓ，２Ｈ）、５．２６（ｄ，１Ｈ，J＝１２．１Ｈｚ）、５．３１（ｄ，１Ｈ，J＝１２．１Ｈｚ） Production Example 2
In Production Example 1, instead of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol, 4- (2-propynyl) -2,3,5,6-tetrafluorobenzyl alcohol was used. In the same way,

4- (2-propynyl) -2,3,5,6-tetrafluorobenzyl = (1S) -cis-2-cyano-2,3,3-trimethylcyclopropanecarboxylate (hereinafter referred to as the compound of the present invention) (Denoted as (2)).
Yellow liquid: ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.27 (s, 3H), 1.49 (s, 3H), 1.50 (s, 3H), 1.62 (s , 1H), 2.07 (t, 1H, J = 2.8 Hz), 3.65 (s, 2H), 5.26 (d, 1H, J = 12.1 Hz), 5.31 (d, 1H) , J = 12.1Hz)

で示される２，３，５，６−テトラフルオロベンジル＝（１Ｓ）−シス−２−シアノ−２，３，３−トリ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（３）と記す）を得る。 Production Example 3
In Production Example 1, the same operation was carried out using 2,3,5,6-tetrafluorobenzyl alcohol instead of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol. formula

2,3,5,6-tetrafluorobenzyl = (1S) -cis-2-cyano-2,3,3-trimethylcyclopropanecarboxylate (hereinafter referred to as the present compound (3)) is obtained. .

で示される４−メチル−２，３，５，６−テトラフルオロベンジル＝（１Ｓ）−シス−３−シアノ−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（４）と記す）を得る。 Production Example 4
In Production Example 1, 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol was used instead of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol, and the same operation was performed. Go to the following formula

4-methyl-2,3,5,6-tetrafluorobenzyl = (1S) -cis-3-cyano-2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as the present compound (4)) Get.

で示される４−メトキシ−２，３，５，６−テトラフルオロベンジル＝（１Ｓ）−シス−２−シアノ−２，３，３−トリ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（５）と記す）を得る。 Production Example 5
In Production Example 1, 4-methoxy-2,3,5,6-tetrafluorobenzyl alcohol was used instead of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol, and the same operation was performed. Go to the following formula

4-methoxy-2,3,5,6-tetrafluorobenzyl = (1S) -cis-2-cyano-2,3,3-trimethylcyclopropanecarboxylate (hereinafter referred to as the present compound (5) and To write).

で示される４−メチルチオメチル−２，３，５，６−テトラフルオロベンジル＝（１Ｓ）−シス−２−シアノ−２，３，３−トリ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（６）と記す）を得る。 Production Example 6
In Preparation Example 1, the same operation was carried out using 4-methylthiomethyl-2,3,5,6-tetrafluorobenzyl alcohol instead of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol. The following formula

4-methylthiomethyl-2,3,5,6-tetrafluorobenzyl = (1S) -cis-2-cyano-2,3,3-trimethylcyclopropanecarboxylate represented by the following formula (6) ).

で示される４−（２−プロペニル）−２，３，５，６−テトラフルオロベンジル＝（１Ｒ）−シス−２−シアノ−２，３，３−トリ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（７）と記す）を得る。 Production Example 7
In Production Example 1, 4- (2-propenyl) -2,3,5,6-tetrafluorobenzyl alcohol was used instead of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol. In the same way,

4- (2-propenyl) -2,3,5,6-tetrafluorobenzyl = (1R) -cis-2-cyano-2,3,3-trimethylcyclopropanecarboxylate (hereinafter referred to as the compound of the present invention) (Denoted as (7)).

で示される２，３，４，５，６−ペンタフルオロベンジル＝（１Ｒ）−シス−２−シアノ−２，３，３−トリ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（８）と記す）と記す）を得る。 Production Example 8
In Production Example 1, the same operation was carried out using 2,3,4,5,6-pentafluorobenzyl alcohol instead of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol. , The following formula

2,3,4,5,6-pentafluorobenzyl = (1R) -cis-2-cyano-2,3,3-trimethylcyclopropanecarboxylate (hereinafter referred to as the present compound (8)) ).

（１Ｒ）−トランス−２，２−ジメチル−３−（２−メチル−1−プロペニル）シクロプロパンカルボン酸２０．０ｇをＴＨＦ１２０ｍＬに溶かし、これにトリエチルアミン１２．７ｇを加えた。該混合物に０℃でオキザリルクロリド１６．０ｇを滴下し、室温で１２時間攪拌した。その後、反応溶液を０℃で２８％アンモニア水４０ｇに注ぎ、室温で２時間攪拌した。該反応溶液を酢酸エチルで抽出し、有機層を水、飽和食塩水の順に洗浄した。該有機層を無水硫酸マグネシウムで乾燥した後、減圧条件下に濃縮し、（１Ｒ）−トランス−２，２−ジメチル−３−（２−メチル−１−プロペニル）シクロプロパンカルボン酸アミド１７．０ｇを得た。
無色結晶：¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）δ（ｐｐｍ）：１．１３(ｓ，３H)、１．１８（ｄ，１Ｈ，J＝５．３Ｈｚ）、１．２６(ｓ，３H)、１．７２（６Ｈ）、２．０８（ｄｄ，１Ｈ，J＝７．７，５．３Ｈｚ）、４．９０（ｄ，１Ｈ，７．７Ｈｚ）、５．３５（ｂｒｓ，１Ｈ）、５．４６（ｂｒｓ，１Ｈ） Next, production examples of production intermediates of this compound are shown in Reference Production Examples.
Reference production example 1

20.0 g of (1R) -trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid was dissolved in 120 mL of THF, and 12.7 g of triethylamine was added thereto. To the mixture, 16.0 g of oxalyl chloride was added dropwise at 0 ° C., and the mixture was stirred at room temperature for 12 hours. Thereafter, the reaction solution was poured into 40 g of 28% aqueous ammonia at 0 ° C. and stirred at room temperature for 2 hours. The reaction solution was extracted with ethyl acetate, and the organic layer was washed with water and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 17.0 g of (1R) -trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid amide. Got.
Colorless crystals: ¹ H-NMR (CDCl ₃ ) δ (ppm): 1.13 (s, 3H), 1.18 (d, 1H, J = 5.3 Hz), 1.26 (s, 3H), 1 .72 (6H), 2.08 (dd, 1H, J = 7.7, 5.3 Hz), 4.90 (d, 1H, 7.7 Hz), 5.35 (brs, 1H), 5.46 (Brs, 1H)

（１Ｒ）−トランス−２，２−ジメチル−３−（２−メチル−１−プロペニル）シクロプロパンカルボン酸アミド１０．０ｇに無水酢酸１６．０ｍＬを加え、室温で３０分攪拌した後、更に１２０℃で３．５時間攪拌した。反応混合物を氷水１５０ｍＬ及び酢酸エチル１２０ｍＬの混合溶液に注ぎ、１時間攪拌した後、有機層を分離し、水層を酢酸エチルでさらに抽出した。得られた有機層を合一し、水、飽和重曹水、飽和食塩水の順に洗浄した。該有機層を無水硫酸マグネシウムで乾燥した後、減圧条件下に濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィーに付し、（１Ｒ）−トランス−２，２−ジメチル−３−（２−メチル−１−プロペニル）シクロプロパンカルボニトリル６．０４ｇを得た。
薄黄色液体：¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）δ（ｐｐｍ）：１．０３（ｄ，１Ｈ，J＝５．１Ｈｚ）、１．１２(ｓ，３H)、１．３５(ｓ，３H)、１．７３（ｓ，６Ｈ）、１．８７（ｄｄ，１Ｈ，J＝７．６，５．２Ｈｚ）、４．８１（ｄ，１Ｈ，J＝７．６Ｈｚ，５．１Ｈｚ） Reference production example 2

To 10.0 g of (1R) -trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid amide, 16.0 mL of acetic anhydride was added, and the mixture was stirred at room temperature for 30 minutes. Stir at 3.5 ° C. for 3.5 hours. The reaction mixture was poured into a mixed solution of 150 mL of ice water and 120 mL of ethyl acetate, stirred for 1 hour, the organic layer was separated, and the aqueous layer was further extracted with ethyl acetate. The obtained organic layers were combined and washed with water, saturated aqueous sodium hydrogen carbonate, and saturated brine in this order. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 6.04 g of (1R) -trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarbonitrile.
Pale yellow _{^{liquid: 1 H-NMR (CDCl 3}} ) δ (ppm): 1.03 (d, 1H, J = 5.1Hz), 1.12 (s, 3H), 1.35 (s, 3H), 1.73 (s, 6H), 1.87 (dd, 1H, J = 7.6, 5.2 Hz), 4.81 (d, 1H, J = 7.6 Hz, 5.1 Hz)

（１Ｒ）−トランス−２，２−ジメチル−３−（２−メチル−１−プロペニル）シクロプロパンカルボニトリル５．７８ｇを無水テトラヒドロフラン６０ｍＬに加え、−７０℃でｎ−ブチルリチウムのｎ−ヘキサン溶液１９．５ｍｌを滴下し、同温で３０分攪拌した後、冷却バスをはずし、２０℃で１時間攪拌した。再び冷却し内温−７０℃でヨウ化メチル９．１２ｇを３０分かけて滴下した。該反応混合物−７０℃で２時間、２０℃で１２時間攪拌した。反応液を冷却した５％塩酸水１００ｍｌに注ぎ、酢酸エチル１００ｍｌで２回抽出した。酢酸エチル層を合わせて、飽和重曹水、食塩水各５０ｍｌで順次洗浄後、得られた有機層を無水硫酸マグネシウムで乾燥した後、減圧条件下に濃縮した後、シリカゲルカラムクロマトにて精製し（展開溶媒：ｎ−ヘキサン／酢酸エチル＝５：１）、（３Ｓ）−トランス、シス−１，２，２−トリメチル−３−（２−メチルプロペニル）シクロプロパンカルボニトリル５．９０ｇを得た。
単黄色液体：¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）（シス／トランス＝２/３）δ（ｐｐｍ）：１．０２（ｓ，６/５Ｈ）、１．１９(ｓ，９/５Ｈ)、１．２１(ｓ，６/５Ｈ)、１．２２(ｓ，９/５Ｈ)、１．３９(ｓ，６/５Ｈ)、１．４１（ｄ，３/５H，Ｊ＝７．２Ｈｚ）、１．４４(ｓ，９/５Ｈ)、１．７０(ｓ，９/５Ｈ)、１．７２（ｓ，６/５Ｈ）、１．７７(ｓ，６/５Ｈ)、１．７８(ｓ，９/５Ｈ)、１．８１（ｄ，２/５，J＝６．８Ｈｚ）、４．７８（ｄ，２/５Ｈ，Ｊ＝６．８Ｈｚ）５．０４（ｄ，３/５Ｈ，Ｊ＝７．２Ｈｚ） Reference production example 3

5.78 g of (1R) -trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarbonitrile was added to 60 mL of anhydrous tetrahydrofuran, and a solution of n-butyllithium in n-hexane at −70 ° C. After adding 19.5 ml dropwise and stirring at the same temperature for 30 minutes, the cooling bath was removed and the mixture was stirred at 20 ° C. for 1 hour. After cooling again, 9.12 g of methyl iodide was added dropwise over 30 minutes at an internal temperature of -70 ° C. The reaction mixture was stirred at -70 ° C for 2 hours and at 20 ° C for 12 hours. The reaction solution was poured into 100 ml of cooled 5% aqueous hydrochloric acid and extracted twice with 100 ml of ethyl acetate. The ethyl acetate layers were combined and washed successively with 50 ml each of saturated aqueous sodium hydrogen carbonate and brine, and the resulting organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography ( Developing solvent: n-hexane / ethyl acetate = 5: 1), (3S) -trans, cis-1,2,2-trimethyl-3- (2-methylpropenyl) cyclopropanecarbonitrile (5.90 g) was obtained.
Single yellow liquid: ¹ H-NMR (CDCl ₃ ) (cis / trans = 2/3) δ (ppm): 1.02 (s, 6 / 5H), 1.19 (s, 9 / 5H), 21 (s, 6 / 5H), 1.22 (s, 9 / 5H), 1.39 (s, 6 / 5H), 1.41 (d, 3 / 5H, J = 7.2 Hz). 44 (s, 9 / 5H), 1.70 (s, 9 / 5H), 1.72 (s, 6 / 5H), 1.77 (s, 6 / 5H), 1.78 (s, 9 / 5H), 1.81 (d, 2/5, J = 6.8 Hz), 4.78 (d, 2 / 5H, J = 6.8 Hz) 5.04 (d, 3 / 5H, J = 7. 2Hz)

（３Ｓ）−トランス、シス−１，２，２−トリメチル−３−（２−メチルプロペニル）シクロプロパンカルボニトリル４５８ｍｇをｔｅｒｔ−ブタノール２０ｍＬ及び水５０ｍＬの混合溶液に加え、これにメタ過ヨウ素酸ナトリウム４．５ｇ及び過マンガン酸カリウム７０ｍｇを加え、室温で３日間攪拌した。該反応混合物を減圧条件下に濃縮し、ｔｅｒｔ−ブタノールを溜去した後、得られた水溶液を酢酸エチルで抽出した。該有機層に５％炭酸カリウム水溶液を加えて攪拌後分液した。得られた水層に５％塩酸を加えてｐＨを３に調製した後、水層を酢酸エチルで抽出した。得られた有機層を無水硫酸マグネシウムで乾燥した後、減圧条件下に濃縮し、（１Ｓ）−トランス、シス−３−シアノ−２，２，３−トリメチルシクロプロパンカルボン酸２１４ｍｇを得た。
単黄色オイル：¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）(シス／トランス=1/1の混合物)δ（ｐｐｍ）：１．３０(ｓ，３/２Ｈ)、１．３１(ｓ，３/２Ｈ)、１．４８(ｓ，３/２Ｈ)、１．５０(ｓ，３/２Ｈ)、１．５２(ｓ，３/２Ｈ)、１．５８(ｓ，３/２Ｈ)、1．６５(ｓ，１/２Ｈ)、１．９９(ｓ，１/２H) Reference production example 4

458 mg of (3S) -trans, cis-1,2,2-trimethyl-3- (2-methylpropenyl) cyclopropanecarbonitrile was added to a mixed solution of 20 mL of tert-butanol and 50 mL of water, and sodium metaperiodate was added thereto. 4.5 g and 70 mg of potassium permanganate were added, and the mixture was stirred at room temperature for 3 days. The reaction mixture was concentrated under reduced pressure to distill off tert-butanol, and the resulting aqueous solution was extracted with ethyl acetate. A 5% aqueous potassium carbonate solution was added to the organic layer, and the mixture was stirred and separated. 5% hydrochloric acid was added to the obtained aqueous layer to adjust the pH to 3, and then the aqueous layer was extracted with ethyl acetate. The obtained organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain 214 mg of (1S) -trans, cis-3-cyano-2,2,3-trimethylcyclopropanecarboxylic acid.
Single yellow oil: ¹ H-NMR (CDCl ₃ ) (mixture of cis / trans = 1/1) δ (ppm): 1.30 (s, 3 / 2H), 1.31 (s, 3 / 2H), 1.48 (s, 3 / 2H), 1.50 (s, 3 / 2H), 1.52 (s, 3 / 2H), 1.58 (s, 3 / 2H), 1.65 (s, 1 / 2H), 1.99 (s, 1 / 2H)

Next, formulation examples are shown. In addition, a part shows a mass part.
Formulation Example 1
20 parts of each of the compounds (1) to (8) of the present invention are dissolved in 65 parts of xylene, 15 parts of Solpol 3005X (Toho Chemical Registration) is added, and the mixture is stirred well to obtain an emulsion.

Formulation Example 2
Solpol 3005X5 parts are added to 40 parts of each of the compounds (1) to (8) of the present invention and mixed well to obtain 32 parts of Carplex # 80 (synthetic hydrous silicon oxide, Shionogi Pharmaceutical registered trademark) and 23 parts of 300 mesh diatomaceous earth. In addition, the mixture is stirred and mixed with a juice mixer to obtain a wettable powder.

Formulation Example 3
1.5 parts of each of the compounds (1) to (8) of the present invention, 1 part of Toxeal GUN (synthetic hydrous silicon oxide, manufactured by Tokuyama Corporation), 2 parts of Liax 85A (sodium lignin sulfonate, manufactured by West vaco chemicals), 30 parts Bentonite Fuji (Bentonite, manufactured by Hojun Co., Ltd.) and 65.5 parts Katsumiyama A clay (Kaolin clay, manufactured by Katsumiyama Mining Co., Ltd.) are thoroughly pulverized and mixed. Granulate and dry to obtain 1.5% granules.

Formulation Example 4
After mixing 10 parts of each of the compounds (1) to (8) of the present invention, 10 parts of phenylxylylethane and 0.5 part of Sumidur L-75 (tolylene diisocyanate, manufactured by Sumitomo Bayer Urethane Co., Ltd.), It is added to 20 parts of a 10% aqueous solution and stirred with a homomixer to obtain an emulsion having an average particle size of 20 μm. 2 parts of ethylene glycol is added thereto, and the mixture is further stirred in a warm bath at 60 ° C. for 24 hours 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 10 parts of each of the compounds (1) to (8) of the present invention and 10 parts of phenylxylylethane were mixed, the mixture was added to 20 parts of a 10% aqueous solution of polyethylene glycol and stirred with a homomixer to obtain an average particle size of 3 μm. To obtain an emulsion. 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. A flowable agent is obtained by mixing 40 parts of the emulsion solution and 60 parts of the thickener solution.

Formulation Example 6
5 parts of each of the compounds (1) to (8) of the present invention were added to Carplex # 80 (synthetic hydrous silicon oxide fine powder, Shionogi Pharmaceutical) and PAP (mixture of monoisopropyl phosphate and diisopropyl phosphate). Add 3 parts and 91.7 parts of talc (300 mesh) and stir and mix with a juice mixer to obtain a powder.

Formulation Example 7
0.1 parts of each of the compounds (1) to (8) of the present invention are dissolved in 10 parts of dichloromethane and mixed with 89.9 parts of deodorized kerosene to obtain an oil agent.

Formulation Example 8
1 part of each of the compounds (1) to (8) 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 a valve part, a propellant (liquefied petroleum oil is passed through the valve part. Gas) 60 parts are pressurized and filled to obtain an oily aerosol.

Formulation Example 9
Each of the compounds (1) to (8) of the present invention (0.6 parts), xylene (5 parts), deodorized kerosene (3.4 parts), and Atmos 300 (emulsifier, registered trademark of Atlas Chemical Co., Ltd.) and water 50 Part is filled into an aerosol container, and 40 parts of propellant (liquefied petroleum gas) is pressurized and filled through a valve part to obtain an aqueous aerosol.

Formulation Example 10
0.3 g of each of the compounds (1) to (8) of the present invention is dissolved in 20 ml of acetone, and this is mixed with a base material for incense sticks (tab powder: rice cake powder: wood powder = 4: 3: 3). After 99.7 g is uniformly stirred and mixed, 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 and dissolved in 0.8 g of each of the compounds (1) to (8) of the present invention and 0.4 g of piperonyl butoxide to make a total of 10 ml. 0.5 ml of this solution was 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 absorbent core (inorganic powder) in which a solution obtained by dissolving 3 parts of each of the compounds (1) to (8) of the present invention in 97 parts of deodorized kerosene is placed in a vinyl chloride container and the upper part can be heated with a heater. Is used to obtain parts for use in a liquid absorption core type heat transpiration apparatus.

Formulation Example 13
100 mg of each of the compounds (1) to (8) 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.

Formulation Example 14
100 μg of each of the compounds (1) to (8) 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. .

Next, it shows as a test example that this invention compound is effective as an active ingredient of a pest control agent.
In the following test examples, the following compounds were used as comparative compounds.
4-methoxymethyl-2,3,5,6-tetrafluorobenzyl = 2,2,3,3-tetramethylcyclopropanecarboxylate (compound described in JP-A-57-165343. Hereinafter, a comparative compound ( A).)

Test example 1
0.025 part of the test compound was dissolved in 10 parts of dichloromethane, and this was mixed with 89.975 parts of deodorized kerosene to prepare a 0.025% oil.
10 German cockroaches (5 males and 5 females) are placed in a test container with a buttered inner wall (diameter: 8.75 cm, height: 7.5 cm, bottom 16 mesh wire mesh), and the container is used for testing. It was installed at the bottom of the chamber (bottom: 46 cm × 46 cm, height: 70 cm). 1.5 ml of each of the compounds (1) to (6) of the present invention was sprayed using a spray gun from a height of 60 cm above the upper surface of the container (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 predetermined time was counted, and the knockdown rate was determined (2 repeated averages).
The results are shown in Table 1.

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

Claims (4)

Formula (1)

[Wherein, R 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 alkyloxy group, a C1-C4 alkyloxymethyl group, or a C1-C4 alkylthiomethyl group. Represents a group. ]
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, which comprises applying an effective amount of the cyclopropanecarboxylic acid ester represented by the formula (1) to pests or habitats of pests. Formula (3)

A cyclopropanecarboxylic acid represented by