JP2009143810A - Cyclopropane carboxylate and use of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound having an excellent pest-controlling effect. <P>SOLUTION: This cyclopropane carboxylate expressed by formula (1) [wherein, R<SP>1</SP>is a 2-4C alkynyl group (e.g. 2-propynyl group) or a 1-4C alkoxymethyl group (e.g. methoxymethyl group)] has the excellent pest-controlling effect. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to certain cyclopropanecarboxylic acid esters and uses thereof.

  Conventionally, various compounds have been synthesized to control pests. For example, Patent Document 1 describes certain types of cyclopropanecarboxylic acid ester derivatives. However, the cyclopropanecarboxylic acid ester derivatives described have not always been sufficiently effective in controlling pests.

PCT International Publication Pamphlet WO81 / 02891

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

〔式中、Ｒ¹はＣ２〜Ｃ４アルキニル基またはＣ１〜Ｃ４アルコキシメチル基を表す。〕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)

[Wherein R ¹ represents a C2 to C4 alkynyl group or a C1 to C4 alkoxymethyl group. ] (Hereinafter referred to as the present compound); a pest control agent characterized by containing the present compound as an active ingredient; an effective amount of the present compound as a pest or harmful Provided is a method for controlling pests characterized by being applied to a habitat of living organisms; and a method for producing 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 compounds of the present invention have two asymmetric carbon atoms on the cyclopropane ring, but the present invention includes all active isomers and isomer mixtures in any ratio.
In the present invention, examples of the C2 to C4 alkynyl group include 2-propynyl group and 2-butenyl group, and examples of the C1 to C4 alkoxymethyl group include methoxymethyl group and ethoxymethyl group.

式（１）において、シクロプロパン環１位の絶対立体配置がＲ配置である化合物；
式（１）において、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がトランス配置である化合物；
式（１）において、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がシス配置である化合物；
式（１）において、シクロプロパン環１位の絶対立体配置がＲ配置であり、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がトランスである化合物；
式（１）において、シクロプロパン環１位の絶対立体配置がＲ配置であり、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がシスである化合物；
式（１）において、シクロプロパン環１位の絶対立体配置がＲ配置であり、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がトランスであるものに富む化合物；
式（１）において、シクロプロパン環１位の絶対立体配置がＲ配置であり、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がトランスであるものが８０％以上である化合物；
式（１）において、シクロプロパン環１位の絶対立体配置がＲ配置であり、シクロプロパン環１位の置換基とシクロプロパン環３位の置換基との相対立体配置がトランスであるものが９０％以上である化合物； Examples 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 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 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), compounds wherein R ¹ is a C2 to C4 alkynyl group;
In the formula (1), compounds wherein R ¹ is a 2-propynyl group;
In the formula (1), compounds wherein R ¹ is a 2-propynyl group, and the absolute configuration at the 1-position of the cyclopropane ring is the R configuration;
In the formula (1), compounds wherein R ¹ is a 2-propynyl group, 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 a trans configuration;
In the formula (1), compounds wherein R ¹ is a 2-propynyl group 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 a cis configuration;
In the formula (1), R ¹ is a 2-propynyl group, the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, and the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring Compounds whose relative configuration is trans;
In the formula (1), R ¹ is a 2-propynyl group, the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, and the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring A compound whose relative configuration is cis;
In the formula (1), R ¹ is a 2-propynyl group, the absolute configuration at the 1-position of the cyclopropane ring is the R configuration, and the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring Compounds rich in those whose relative configuration is trans;

In the formula (1), compounds wherein R ¹ is a C1 to C4 alkoxymethyl group;
In the formula (1), compounds wherein R ¹ is a methoxymethyl group;
In the formula (1), compounds wherein R ¹ is a methoxymethyl group and the absolute configuration at the 1-position of the cyclopropane ring is the R configuration;
In the formula (1), compounds wherein R ¹ is a methoxymethyl group, 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 a trans configuration;
In the formula (1), compounds wherein R ¹ is a methoxymethyl group 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 a cis configuration;
In the formula (1), R ¹ is a methoxymethyl group, the absolute configuration at the 1-position of the cyclopropane ring is the R-configuration, and the relative relationship between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring A compound whose configuration is trans;
In the formula (1), R ¹ is a methoxymethyl group, the absolute configuration at the 1-position of the cyclopropane ring is the R-configuration, and the relative relationship between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring A compound whose configuration is cis;
In the formula (1), R ¹ is a methoxymethyl group, the absolute configuration at the 1-position of the cyclopropane ring is the R-configuration, and the relative relationship between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring A compound rich in steric configuration.

〔式中、Ｒ¹はＣ２〜Ｃ４アルキニル基またはＣ１〜Ｃ４アルコキシメチル基を表す。〕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とを反応させる方法。
本反応は通常、縮合剤および塩基の存在下、もしくは酸触媒の存在下に行われる。また、本反応は通常、溶媒中で行なわれる。本反応に用いら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、１−エチル−３−（３−ジメチルアミノプロピル）カルボジイミドハイドロクロライド等が挙げられる。本反応に用いられる塩基としては、例えばトリエチルアミン、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。本反応に用いられる酸触媒としては、例えば硫酸等の無機酸、パラトルエンスルホン酸、メタンスルホン酸等のスルホン酸等が挙げられる。本反応に用いられる溶媒は、反応において不活性な溶媒を用いることができ、具体的には例えばトルエン、ヘキサン等の炭化水素、ジエチルエーテル、テトラヒドロフラン等のエーテル、クロロホルム、ジクロロメタン、１、２−ジクロロエタン等のハロゲン化炭化水素、及びこれらの混合溶媒を挙げることができる。
本反応の反応時間は通常、瞬時〜７２時間の範囲であり、反応温度は通常−２０℃〜１００℃の範囲である。
本反応に用いられる式（２）で示されるアルコール化合物の量は、式（３）で示されるカルボン酸１モルに対して、１モルが理論量であるが、通常０．５〜１．５モルの範囲で適宜選択することができる。
本反応を縮合剤の存在下に行う場合、反応に用いられる縮合剤の量は、式（３）で示されるカルボン酸１モルに対して、通常１モルであるが、反応の状況に応じて適宜変化させることができる。また、反応に用いられる塩基の量は、式（３）で示されるカルボン酸１モルに対して、通常０．１〜１モルの範囲である。
本反応を酸触媒の存在下に行う場合、反応に用いられる酸触媒の量は、式（３）で示されるカルボン酸１モルに対して、通常０．０１〜２０モルの範囲であり、反応の状況に応じて適宜変化させることができる。
本反応の終了後は、反応混合物を水に注加し有機溶媒抽出した後に濃縮する等の通常の後処理操作を行うことによって、本発明化合物を単離することができる。また、必要であれば、単離された本発明化合物を、クロマトグラフィー、蒸留等の精製操作に付すことにより、本発明化合物を精製することもできる。 The compound of the present invention can be produced, for example, by the production method shown below.
[Production method 1]
Formula (2)

[Wherein R ¹ represents a C2 to C4 alkynyl group or a C1 to C4 alkoxymethyl group. An alcohol compound represented by formula (3)

The method of making it react with carboxylic acid shown by this.
This reaction is usually performed in the presence of a condensing agent and a base, or in the presence of an acid catalyst. Moreover, this reaction is normally performed in a solvent. Examples of the condensing agent used in this reaction include dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and the like. Examples of the base used in this reaction include organic bases such as triethylamine, pyridine, N, N-diethylaniline, 4-dimethylaminopyridine, diisopropylethylamine and the like. Examples of the acid catalyst used in this reaction include inorganic acids such as sulfuric acid, and sulfonic acids such as p-toluenesulfonic acid and methanesulfonic acid. As the solvent used in this reaction, an inert solvent 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.
The reaction time of this reaction 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.
The amount of the alcohol compound represented by the formula (2) used in this reaction is a theoretical amount per mole of the carboxylic acid represented by the formula (3), but is usually 0.5 to 1.5. It can select suitably in the range of a mole.
When this reaction is carried out in the presence of a condensing agent, the amount of the condensing agent used in the reaction is usually 1 mol per 1 mol of the carboxylic acid represented by formula (3), but depending on the situation of the reaction It can be changed appropriately. Moreover, the quantity of the base used for reaction is the range of 0.1-1 mol normally with respect to 1 mol of carboxylic acids shown by Formula (3).
When this reaction is carried out in the presence of an acid catalyst, the amount of the acid catalyst used in the reaction is usually in the range of 0.01 to 20 mol with respect to 1 mol of the carboxylic acid represented by formula (3). It can be appropriately changed according to the situation.
After completion of this reaction, the compound of the present invention can be isolated by carrying out usual post-treatment operations such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating. If necessary, the compound of the present invention can also be purified by subjecting the isolated compound of the present invention to purification operations such as chromatography and distillation.

[Production method 2]
A method of reacting an alcohol compound represented by the formula (2) with a reactive derivative of a carboxylic acid represented by the formula (3) (that is, acid halide, acid anhydride, etc.).
This reaction is usually performed in the presence of a base. Moreover, this reaction is normally performed in a solvent. Examples of the base used in this reaction include organic bases such as triethylamine, pyridine, N, N-diethylaniline, 4-dimethylaminopyridine, diisopropylethylamine and the like. As the solvent used in this reaction, an inert solvent 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.
The reaction time of this reaction 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.
The amount of the alcohol compound represented by the formula (2) used in this reaction is a theoretical amount of 1 mol with respect to 1 mol of the reactive derivative of the carboxylic acid represented by the formula (3). It can select suitably in the range of -2.0 mol. The amount of the base used in this reaction is usually 1 mole per 1 mole of the reactive derivative of the carboxylic acid represented by formula (3), but can be appropriately changed depending on the reaction situation. .
After completion of this reaction, the compound of the present invention can be isolated by carrying out usual post-treatment operations such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating. If necessary, the compound of the present invention can also be purified by subjecting the isolated compound of the present invention to purification operations such as chromatography and distillation.

  The alcohol compound represented by the formula (2) is described in JP-A-56-97251, JP-A-57-123146, JP-A-61-207361, JP-A-11-222463, and the like. It can be a compound or can be produced according to the methods described in these documents.

〔式中、Ｒ¹は前記と同じ意味を表す。〕
で示されるアルデヒド化合物と、フッ素化剤とを反応させることにより製造することができる。
該反応は通常、溶媒の存在下に行われる。用いられる溶媒としては、例えば塩化メチレン、クロロホルムなどのハロゲン化炭化水素、トルエン、ヘキサン等の炭化水素、及びそれらの混合物が挙げられる。
反応に用いられるフッ素化剤としては、例えば（ジメチルアミノ）サルファー＝トリフルオリド〔(dimethylamino)sulfur trifluoride〕、（ジエチルアミノ）サルファー＝トリフルオリド〔(diethylamino)sulfur trifluoride〕等が挙げられる。用いられるフッ素化剤の量は、式（４）で示される化合物に対して、通常２〜６当量の範囲である。
該反応の反応時間は通常、１〜２４時間の範囲であり、反応温度は通常室温〜１００℃の範囲である。
反応終了後は、反応混合物を水に注加し有機溶媒抽出した後に濃縮する等の通常の後処理操作を行うことによって、本発明化合物で示される化合物を単離することができる。また、必要であれば、単離された本発明化合物を、クロマトグラフィー、蒸留等の精製操作に付すことにより、本発明化合物を精製することもできる。 The compound of the present invention can also be produced by (Production Method 3) or the like.
[Production method 3]
Formula (4)

[Wherein R ¹ represents the same meaning as described above. ]
It can manufacture by making the aldehyde compound shown by and a fluorinating agent react.
The reaction is usually performed in the presence of a solvent. Examples of the solvent used include halogenated hydrocarbons such as methylene chloride and chloroform, hydrocarbons such as toluene and hexane, and mixtures thereof.
Examples of the fluorinating agent used in the reaction include (dimethylamino) sulfur trifluoride ((dimethylamino) sulfur trifluoride) and (diethylamino) sulfur trifluoride ((diethylamino) sulfur trifluoride). The amount of the fluorinating agent used is usually in the range of 2 to 6 equivalents relative to the compound represented by the formula (4).
The reaction time of the reaction is usually in the range of 1 to 24 hours, and the reaction temperature is usually in the range of room temperature to 100 ° C.
After completion of the reaction, the compound represented by the compound of the present invention can be isolated by carrying out a usual post-treatment operation such as pouring the reaction mixture into water and extracting it with an organic solvent and then concentrating. If necessary, the compound of the present invention can also be purified by subjecting the isolated compound of the present invention to purification operations such as chromatography and distillation.

  The compound represented by the formula (4) can be produced according to the method described in JP-A No. 2002-212138.

  Isomers derived from two asymmetric carbon atoms present on the cyclopropane ring of the compound of the present invention, that is, (1R) -trans isomer, (1S) -trans isomer, (1R) -cis isomer and (1S)- Cis isomer {where (1R) and (1S) mean position and absolute configuration on the cyclopropane ring, trans and cis mean relative configuration of the 1- and 3-positions on the cyclopropane ring . } Can be produced from the corresponding carboxylic acid represented by the formula (3) (or a reactive derivative thereof) or an isomer of the aldehyde compound represented by the formula (4).

  Moreover, the carboxylic acid shown by Formula (3) can be manufactured by the method shown below, for example.

・式（５）で示される化合物 → 式（６）で示される化合物
式（６）で示される化合物は、式（５）で示される化合物とフッ素化剤とを反応させることにより製造することができる。
該反応は通常、溶媒の存在下に行われる。用いられる溶媒としては、例えば塩化メチレン、クロロホルムなどのハロゲン化炭化水素、トルエン、ヘキサン等の炭化水素、及びそれらの混合物が挙げられる。
反応に用いられるフッ素化剤としては、例えば（ジメチルアミノ）サルファー＝トリフルオリド〔(dimethylamino)sulfur trifluoride〕、（ジエチルアミノ）サルファー＝トリフルオリド〔(diethylamino)sulfur trifluoride〕等が挙げられる。用いられるフッ素化剤の量は、式（５）で示される化合物に対して、通常２〜６当量の範囲である。
該反応の反応時間は通常、１〜２４時間の範囲であり、反応温度は通常室温〜１００℃の範囲である。
反応終了後は、反応混合物を水に注加し有機溶媒抽出した後に濃縮する等の通常の後処理操作を行うことによって、式（６）で示される化合物を単離することができる。また、必要であれば、単離された本発明化合物を、クロマトグラフィー、蒸留等の精製操作に付すことにより、本発明化合物を精製することもできる。

Compound represented by formula (5) → compound represented by formula (6) The compound represented by formula (6) can be produced by reacting the compound represented by formula (5) with a fluorinating agent. it can.
The reaction is usually performed in the presence of a solvent. Examples of the solvent used include halogenated hydrocarbons such as methylene chloride and chloroform, hydrocarbons such as toluene and hexane, and mixtures thereof.
Examples of the fluorinating agent used in the reaction include (dimethylamino) sulfur trifluoride [(dimethylamino) sulfur trifluoride], (diethylamino) sulfur trifluoride [(diethylamino) sulfur trifluoride], and the like. The amount of the fluorinating agent used is usually in the range of 2 to 6 equivalents relative to the compound represented by the formula (5).
The reaction time of the reaction is usually in the range of 1 to 24 hours, and the reaction temperature is usually in the range of room temperature to 100 ° C.
After completion of the reaction, the compound represented by the formula (6) can be isolated by carrying out a usual post-treatment operation such as pouring the reaction mixture into water, extracting the mixture with an organic solvent, and then concentrating. If necessary, the compound of the present invention can also be purified by subjecting the isolated compound of the present invention to purification operations such as chromatography and distillation.

Compound represented by formula (6) → Carboxylic acid represented by formula (3) The carboxylic acid represented by formula (3) is produced by hydrolyzing the compound represented by formula (6) in the presence of a base. be able to.
The reaction can be performed in the presence of a solvent. Examples of the solvent used include alcohols such as methanol and ethanol, 1,4-dioxane, water, and mixtures thereof.
Examples of the base used for the reaction include sodium hydroxide and potassium hydroxide. The amount of the base used is usually 1 mol to an excess amount with respect to 1 mol of the compound represented by the formula (6).
The reaction time of the reaction is usually in the range of 1 to 24 hours, and the reaction temperature is usually in the range of room temperature to 150 ° C.
After completion of the reaction, the carboxylic acid represented by the formula (3) can be isolated by performing post-treatment operations such as adding an acid to the reaction mixture to make it acidic, extracting with an organic solvent, and concentrating.

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. Coleoptera: Coleoptera 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 Kona leopard mite, Yake leopard mite 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 transpiration insecticides, etc.), piezo-type insecticide preparations, 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.), substances that are solid 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 resins such as density polyethylene; ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymers; ethylene-methyl methacrylate copolymers; 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-acrylic Ethylene-vinylcarboxylic acid copolymers such as acid copolymers; ethylene-tetracyclododecene copolymers; polypropylene resins such as propylene homopolymers and propylene-ethylene copolymers; poly-4-methylpentene-1 , Polybutene-1, polybutadiene, polystyrene; acrylonitrile-styrene resin; styrene-based elastomer such as acrylonitrile-butadiene-styrene resin, styrene-conjugated diene block copolymer, hydrogenated styrene-conjugated diene block copolymer; fluorine resin; Polymethacryl Acrylic resins such as methyl; polyamide resins such as nylon 6 and nylon 66; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polycyclohexylene dimethylene terephthalate; polycarbonate, polyacetal, polyacrylic Phon, 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, metal, Felts, fibers, fabrics, knitted fabrics, sheets, papers, threads, foams, porous bodies and multifilaments composed of one or more ceramics That.

  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 Butadiene, polystyrene, acrylonitrile-styrene resin; styrene-based elastomers such as acrylonitrile-butadiene-styrene resin, styrene-conjugated diene copolymer, styrene-conjugated diene block copolymer hydrogenated product; fluororesin; 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 further processed into a plate shape, a film shape, a tape shape, a net shape, a string shape or the like through steps such as molding and cutting if necessary. These resin preparations are processed, for example, as 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 fragrances such as cheese fragrance, onion fragrance, and peanut oil.

The pest control method of the present invention is carried out by applying an effective amount of the compound of the present invention to a pest or a pest habitat, usually in the form of the pest control agent of the present invention.
Examples of the application method of the pest control agent of the present invention include the following methods, which can be appropriately selected depending on the form, use place, etc. of the pest control agent of the present invention.
(1) A method of treating the pest control agent of the present invention as it is in a pest or a habitat of the pest.
(2) A method in which the pest control agent of the present invention is diluted with a solvent such as water and then sprayed to a pest or a habitat of the pest.
In this case, the pest control agent of the present invention formulated in an emulsion, wettable powder, flowable agent, microcapsule preparation or the like is usually diluted so that the concentration of the compound of the present invention becomes 0.1 to 10,000 ppm. .
(3) A method 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 pesticidal composition of the present invention is used for controlling ectoparasites of domestic animals such as cattle, horses, pigs, sheep, goats and chickens, and small animals such as dogs, cats, rats and mice, it is well known in veterinary medicine. Can be used on animals in any way. As a specific method of use, for the purpose of systemic control, for example, it is administered by tablet, feed mixing, suppository, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.) For purposes of non-systemic control, for example, spraying oils or aqueous solutions, pour-on or spot-on treatment, washing animals with shampoo formulations or It is used by a method such as attaching a resin transpiration agent to an animal using a collar or ear tag. The amount of the compound of the present invention when administered to an animal body is usually in the range of 0.01 to 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, for example, dichlorvos, fenitrothion, cyanophos, propenophos, sulprophos, phentoate, isoxathion, tetrachlorobinphos, fenthion, chlorpyrifos, diazinon, acephate, terbufos, folate, chlorethoxyphos, Organophosphorus compounds such as phostiazate, etoprophos, kazusafos, metidathion, disulfotone, dioxabenzophos, dimethoate, phentoate, malathion, trichlorfone, azinephosmethyl, monocrotophos, ethion;
Carbamate compounds such as propoxyl, carbaryl, methoxadiazone, fenocarb, mesomil, thiodicarb, alanib, benfuracarb, oxamyl, aldicarb, methiocarb, carbosulfan, etiophencarb, phenothiocarb, cartap;
Allethrin, tetramethrin, plaretrin, d-phenothrin, d-resmethrin, ciphenothrin, permethrin, cypermethrin, alpha cypermethrin, zetacivermethrin, deltamethrin, tralomethrin, cyfluthrin, beta cyfluthrin, cyhalothrin, lambda cihalothrin, d- Furamethrin, imiprothrin, etofenprox, fenvalerate, esfenvalerate, fenpropatrin, silafluophene, bifenthrin, transfluthrin, flucitrinate, taufulvalinate, acrinathrin, tefluthrin, cycloprotorin, methofurtrin, profluthrin, dipentfurin Flumetrine, fulvalinate, 2-methyl-2- (4-bromodifluoromethoxyphenyl) Yl) propyl (3-phenoxybenzyl) d - ether, 5- (2-propynyl) furfuryl 2,2,3,3-tetramethyl-cyclopropanecarboxylate pyrethroid compounds such rate;
Neonicotinoid compounds such as acetamiprid, nitenpyram, thiacloprid, thiamethoxam, dinotefuran, clothianidin, imidacloprid;
Chlorinated hydrocarbon compounds such as endosulfan, γ-BHC, 1,1-bis (chlorophenyl) -2,2,2-trichloroethanol;
Benzoylphenylurea compounds such as lufenuron, chlorfluazuron, hexaflumuron, diflubenzuron, triflumuron, teflubenzuron, flufenoxuron, fluazuron, novallon, triazuron, bistrifluron, flufenoxuron;
Juvenile hormone-like substances such as pyriproxyfen, metoprene, hydroprene, phenoxycarb;
Phenylpyrazole compounds such as acetoprole, pyriprole, pyrafluoprol, ethiprole;
Benzoylhydrazine compounds such as tebufenozide, chromafenozide, methoxyphenozide, halofenozide;
Macrolide compounds such as polynactin complex [tetranactin, ginactin, trinactin], abamectin, emamectin benzoate, spinosad, ivermectin, azadirachtin, milbemectin;
Diafenthiuron, pymetrozine, flonicamid, triazamate, buprofezin, spinosad, emamectin benzoate, chlorfenapyr, indoxacarb MP, pyridalyl, cyromazine, fenpyroximate, tebufenpyrad, tolfenpyrad, pyridaben, pyrimidifene, flucripyrixetoxazol, ethaquinoxex , Clofentezine, fenbutasine oxide, dicophor, propargite, abamectin, evermectin, milbemectin, amitraz, bensultap, thiocyclam, endosulfan, spirodiclofen, spiromesifen, amidoflumet and azadirachtin, bromopropyrate, tetradiphone, quinomethionate, polynactin complex [ Toranakuchin, Jinakuchin, Torinakuchin], abamectin, metaflumizone, flubendiamide, chlorantraniliprole, pyrifluquinazon, and the like.

  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 (piperonyl butoxide).

  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−（２−プロピニル）−２，３，５，６−テトラフルオロベンジル＝（１Ｒ）−トランス−３−ジフルオロメチル−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）１６６ｍｇを無色透明液体として得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）δ（ｐｐｍ）：１．２６（３Ｈ，ｓ），１．２８（３Ｈ，ｓ），１．８０−１．８２（１Ｈ，ｍ），１．８８−１．９６（１Ｈ，ｍ），２．０７−２．０８（１Ｈ，ｍ），３．６５（２Ｈ，ｔ，Ｊ＝１．３Ｈｚ），５．２５（２Ｈ，ｓ），５．６１（１Ｈ，ｄｔ，Ｊ＝６．１，５５．９Ｈｚ） First, the manufacture example of this invention compound is shown.
Production Example 1
166 mg (0.76 mmol) of 4- (2-propynyl) -2,3,5,6-tetrafluorobenzyl alcohol and 150 mg of (1R) -trans-3-difluoromethyl-2,2-dimethylcyclopropanecarboxylic acid (0 (.91 mmol) in chloroform (5 mL) was added 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (174 mg, 0.91 mmol) and 4-dimethylaminopyridine (5 mg), and the mixture was stirred at room temperature for 18 hours. Water was poured into 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. The residue was subjected to silica gel column chromatography,

4- (2-propynyl) -2,3,5,6-tetrafluorobenzyl = (1R) -trans-3-difluoromethyl-2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as the present compound ( 1) 166 mg was obtained as a colorless transparent liquid.
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.26 (3H, s), 1.28 (3H, s), 1.80-1.82 (1H, m), 1.88-1. 96 (1H, m), 2.07-2.08 (1H, m), 3.65 (2H, t, J = 1.3 Hz), 5.25 (2H, s), 5.61 (1H, dt, J = 6.1, 55.9 Hz)

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＝（１Ｒ）−トランス−３−ジフルオロメチル−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（２）と記す）１８２ｍｇを無色透液体として得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）δ（ｐｐｍ）：１．２５（３Ｈ，ｓ），１．２８（３Ｈ，ｓ），１．８０−１．８２（１Ｈ，ｍ），１．８８−１．９５（１Ｈ，ｍ）、３．４１（３Ｈ，ｓ），４．５９（２Ｈ，ｓ），５．２６（２Ｈ，ｍ）、５．６３（１Ｈ，ｄｔ，Ｊ＝６．２，５５．９Ｈｚ） Production Example 2
273 mg (1.2, 2 mmol) of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol and 240 mg (1.R) -trans-3-difluoromethyl-2,2-dimethylcyclopropanecarboxylic acid (46 mmol) in chloroform (5 mL) was added 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (335 mg, 1.75 mol and 4-dimethylaminopyridine (5 mg)), and the mixture was stirred at room temperature for 18 hours. Water was added, and the mixture was extracted with ethyl acetate.The organic layer was dried over magnesium sulfate and concentrated under reduced pressure.The residue was subjected to silica gel column chromatography and represented by the following formula.

4-methoxymethyl-2,3,5,6-tetrafluorobenzyl = (1R) -trans-3-difluoromethyl-2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as the present compound (2)) 182 mg was obtained as a colorless permeable liquid.
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.25 (3H, s), 1.28 (3H, s), 1.80-1.82 (1H, m), 1.88-1. 95 (1H, m), 3.41 (3H, s), 4.59 (2H, s), 5.26 (2H, m), 5.63 (1H, dt, J = 6.2, 55. 9Hz)

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＝（１Ｒ）−シス−３−ジフルオロメチル−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（３）と記す）１７９ｍｇを無色透液体として得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ3）δ（ｐｐｍ）：１．２４（３Ｈ，ｓ），１．３３（３Ｈ，ｓ），１．５６−１．８０（２Ｈ，ｍ），３．４１（３Ｈ，ｓ）、４．５９（２Ｈ，ｓ），５．２１−５．２９（２Ｈ，ｍ）、６．１２−６．４２（１Ｈ，ｍ） Production Example 3
To 20 mL of a chloroform solution of 400 mg (1.15 mmol) of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl = (1R) -cis-3-formyl-2,2-dimethylcyclopropanecarboxylate, dimethylamino Sulfur = trifluoride 0.3 mL (2.30 mmol) was added at 0 ° C., and the mixture was further 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 concentrated under reduced pressure. The residue was subjected to silica gel column chromatography,

4-methoxymethyl-2,3,5,6-tetrafluorobenzyl = (1R) -cis-3-difluoromethyl-2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as the present compound (3) and 179 mg was obtained as a colorless permeable liquid.
¹ H-NMR (CDCl 3) δ (ppm): 1.24 (3H, s), 1.33 (3H, s), 1.56-1.80 (2H, m), 3.41 (3H, s ), 4.59 (2H, s), 5.21-5.29 (2H, m), 6.12-6.42 (1H, m)

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＝（１Ｒ）−シス−３−ジフルオロメチル−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（４）と記す）を得る。 Production Example 4
In Production Example 3, instead of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl = (1R) -cis-3-formyl-2,2-dimethylcyclopropanecarboxylate, 4- (2- Propinyl) -2,3,5,6-tetrafluorobenzyl = (1R) -cis-3-formyl-2,2-dimethylcyclopropanecarboxylate

4- (2-propynyl) -2,3,5,6-tetrafluorobenzyl = (1R) -cis-3-difluoromethyl-2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as the present compound ( 4)) is obtained.

メチル＝（１Ｒ）−トランス−３−ホルミル−２，２−ジメチルシクロプロパンカルボキシレート１．０ｇ(６．４０ｍｍｏｌ)のクロロホルム溶液１５ｍＬに、ジメチルアミノサルファー＝トリフルオリド２．１ｍＬ(１６．０ｍｍｏｌ)を0℃で加え、室温で１８時間攪拌した。該反応混合物に水を加え、酢酸エチルで抽出した。該有機層を硫酸マグネシウムで乾燥した後、減圧条件下に濃縮して、メチル＝（１Ｒ）−トランス−３−ジフルオロメチル−２，２−ジメチルシクロプロパンカルボキシレート９２６ｍｇを得た。¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）δ（ｐｐｍ）：１．２６（３Ｈ，ｓ），１．２８（３Ｈ，ｓ），１．７７−１．９４（２Ｈ，ｍ），３．７１（３Ｈ，ｓ），５．６２（１Ｈ，ｄｔ，Ｊ＝６.３，５６．０Ｈｚ） Next, production examples of production intermediates of this compound are shown in Reference Production Examples.
Reference production example 1

To 15 mL of a chloroform solution of 1.0 g (6.40 mmol) of methyl = (1R) -trans-3-formyl-2,2-dimethylcyclopropanecarboxylate, 2.1 mL (16.0 mmol) of dimethylaminosulfur trifluoride was added. It added at 0 degreeC 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 concentrated under reduced pressure to obtain 926 mg of methyl = (1R) -trans-3-difluoromethyl-2,2-dimethylcyclopropanecarboxylate. ¹ H-NMR (CDCl ₃ ) δ (ppm): 1.26 (3H, s), 1.28 (3H, s), 1.77-1.94 (2H, m), 3.71 (3H, s), 5.62 (1H, dt, J = 6.3, 56.0 Hz)

メチル＝（１Ｒ）−トランス−３−ジフルオロメチル−２，２−ジメチルシクロプロパンカルボキシレート９２６ｍｇ(５．２０ｍｍｏｌ)のメタノール５ｍＬと５％NaOH水溶液２０ｍＬを加え、１００℃で５時間攪拌した。該反応混合物にメチルーｔｅｒｔ−ブチルエーテルを加え、分液した後、水層を１Ｎ塩酸にてｐＨを２に調整し、酢酸エチルで抽出した。得られた有機層を硫酸マグネシウムで乾燥した後、減圧条件下に濃縮して、（１Ｒ）−トランス−３−ジフルオロメチル−２，２−ジメチルシクロプロパンカルボン酸８６１ｍｇを得た。
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）δ（ｐｐｍ）：１．３０（３Ｈ，ｓ）、１．３１（３Ｈ，ｓ），１．５９（ｂｒｓ，１Ｈ）、１．８３−１．９６（２Ｈ，ｍ），５．６４（１Ｈ，ｄｔ，Ｊ＝６.０，５５．９Ｈｚ） Reference production example 2

Methyl (1R) -trans-3-difluoromethyl-2,2-dimethylcyclopropanecarboxylate (926 mg, 5.20 mmol) in methanol (5 mL) and 5% NaOH aqueous solution (20 mL) were added, and the mixture was stirred at 100 ° C. for 5 hours. Methyl tert-butyl ether was added to the reaction mixture and the phases were separated, and the aqueous layer was adjusted to pH 2 with 1N hydrochloric acid and extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate and concentrated under reduced pressure to obtain 861 mg of (1R) -trans-3-difluoromethyl-2,2-dimethylcyclopropanecarboxylic acid.
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.30 (3H, s), 1.31 (3H, s), 1.59 (brs, 1H), 1.83-1.96 (2H, m), 5.64 (1H, dt, J = 6.0, 55.9 Hz)

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 (4) 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
5 parts of Solpol 3005X is added to 40 parts of each of the compounds (1) to (4) of the present invention, and mixed well to mix 32 parts of Carplex # 80 (synthetic hydrous silicon oxide, Shionogi Pharmaceutical registered trademark) and 23 parts of 300 mesh diatomaceous earth. And stirring and mixing with a juice mixer to obtain a wettable powder.

Formulation Example 3
1.5 parts of each of the compounds (1) to (4) 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 (4) 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.), Add to 20 parts of a 10% aqueous solution and 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 each of the compounds (1) to (4) of the present invention and 10 parts of phenylxylylethane, the mixture is 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. 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 each of the compounds (1) to (4) of the present invention was added to Carplex # 80 (synthetic hydrous silicon oxide fine powder, Shionogi Pharmaceutical registered trademark), 3 parts, PAP (mixture of monoisopropyl phosphate and diisopropyl phosphate) 0. 3 parts and 91.7 parts of talc (300 mesh) are added and stirred and mixed with a juice mixer to obtain a powder.

Formulation Example 7
0.1 parts of each of the compounds (1) to (4) of the present invention are dissolved in 10 parts of dichloromethane, and this is 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 (4) 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
0.6 parts of each of the compounds (1) to (4) of the present invention, 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of sorbitan monolaurate (Leodol SP-L10, manufactured by Kao Corporation, HLB: 8.6) An aerosol container is filled with 50 parts of water and 50 parts of water, and 40 parts of a 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 (4) of the present invention is dissolved in 20 ml of acetone, and this is mixed with an incense base material (tab powder: rice cake powder: wood powder = 4: 3: 3). After uniformly mixing with 99.7 g, 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 (4) of the present invention and 0.4 g of piperonyl butoxide 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 absorbent core (inorganic powder) in which a solution obtained by dissolving 3 parts of each of the compounds (1) to (4) 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 (4) 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 (4) of the present invention is dissolved in an appropriate amount of acetone, 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４−（２−プロピニル）−２，３，５，６−テトラフルオロベンジル＝（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（特開昭６１−２０７３６１号公報に記載の化合物。以下、比較化合物（Ａ）と記す。）
・下記式

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＝（１Ｒ）−トランス−２，２，３−トリメチルシクロプロパンカルボキシレート（特開２００１−３０２５９０号公報に記載の化合物。以下、比較化合物（Ｂ）と記す。）
・下記式

で示される７−トリフルオロメチル−２，３−ジヒドロベンゾフラン−３−イル＝（１Ｒ）−トランス−３−ジフルオロメチル−２，２−ジメチルシクロプロパンカルボキシレート（ＰＣＴ国際出願パンフレットＷＯ８１／０２８９２に記載の化合物。以下、比較化合物（Ｘ）と記す。） 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.
・ The following formula

4- (2-propynyl) -2,3,5,6-tetrafluorobenzyl represented by the formula: (1R) -trans-3- (2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate (Compound described in JP-A-61-207361. Hereinafter, referred to as comparative compound (A).)
・ The following formula

4-methoxymethyl-2,3,5,6-tetrafluorobenzyl = (1R) -trans-2,2,3-trimethylcyclopropanecarboxylate (a compound described in JP 2001-302590 A). Hereinafter, referred to as comparative compound (B).)
・ The following formula

7-trifluoromethyl-2,3-dihydrobenzofuran-3-yl = (1R) -trans-3-difluoromethyl-2,2-dimethylcyclopropanecarboxylate represented by the formula (PCT International Application Pamphlet WO81 / 02892 (Hereinafter referred to as Comparative Compound (X))

Test example 1
Test example Knock-down test with incense stick against squid A prepared 1% (w / v) acetone solution of the test compound, and uniformly impregnating 0.3 g of the incense base material (manufactured by UI Katori Co., Ltd.) with 0.3 g of the incense stick base material And then air-dried to produce a test fragrance. After igniting one end of the test incense stick and confirming that combustion was stabilized after one minute of ignition, the test incense stick was installed in the center of the floor in a cube chamber of 70 cm on a side where 20 adult female mosquitoes were released. . The incense sticks were burned in the chamber for 30 seconds after installation, and then immediately removed, and the number of squids knocked down after 3 minutes was investigated (one iteration).
The results are shown in Table 1.

Test example 2
A 0.005% (w / v) acetone solution of the test compound was prepared. The acetone solution was treated on the chest dorsum of female mosquitoes so that the amount of the test compound was 0.015 μg / head. Thereafter, water and food were given to the test insects, and the number of individuals who died after 24 hours was investigated to determine the death rate (2 repetitions).
The results are shown in Table 2.

  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 ¹ represents a C2 to C4 alkynyl group or a C1 to C4 alkoxymethyl group. ]
A cyclopropanecarboxylic acid ester represented by The cyclopropanecarboxylic acid ester according to claim ¹ , wherein R ¹ in formula (1) is a 2-propynyl group or a methoxymethyl group. 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.