JP2003206264A - Ester compound and application of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a compound having excellent pest control effect and a pest control material containing the compound as an effective ingredient and provide a pest control method for applying the compound to the pest or a habitat of the pest. <P>SOLUTION: This ester compound is expressed by formula (1) [wherein R<SP>1</SP>and R<SP>2</SP>express, e.g. (A)R<SP>1</SP>expresses a 1-6C alkyl and R<SP>2</SP>expresses a 3-6C alkenyl, a 3-6C alkynyl or a 2-6C haloalkyl]. The pest control material contains the compound as the effective ingredient. This pest control method is to apply the compound to the pest or the habitat of the pest. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ester compound and its use.

[0002]

DISCLOSURE OF THE INVENTION The present invention provides a compound having an excellent pest control effect, a pest control agent containing the compound as an active ingredient, and a pest control agent containing the compound. It is an object to provide a pest control method characterized by being applied to a habitat.

[0003]

Means for Solving the Problems As a result of extensive studies by the present inventors to find a compound having an excellent pest controlling effect, the ester compound represented by the following formula (1) has an excellent pest controlling effect. And completed the present invention.

That is, the present invention uses the formula (1) [Wherein, R ¹ and R ² are (A), (B) or (C). (A) R ¹ represents a hydrogen atom or a C1-C6 alkyl group, and R ² represents a C3-C6 alkenyl group, a C3-C6 alkynyl group or a C2-C6 haloalkyl group. (B) R ¹ represents a methyl group or an ethyl group, and R ² represents an ethyl group or a propyl group. ; (C) R ¹
And R ² are bonded at the terminal to represent an ethylene group, a trimethylene group, or a tetramethylene group. ] The pest control agent characterized by containing the ester compound shown by these (henceforth compound of this invention), this invention compound as an active ingredient, and this invention compound is applied to a pest or a habitat of a pest. A method for controlling pests is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention includes an isomer derived from two asymmetric carbons on a cyclopropane ring and an isomer derived from a carbon-carbon double bond optionally present in a carboxylic acid moiety. Although present, the present invention includes each and mixtures thereof. In the compound of the present invention, the absolute configuration at the 1-position of the cyclopropane ring is R from the viewpoint of pest control efficacy.
An isomer mixture rich in a compound having a configuration or a compound having an R-configuration in the absolute configuration at the 1-position of the cyclopropane ring is preferable, and in particular, the absolute configuration at the 1-position of the cyclopropane ring is in the R-configuration and the cyclopropane ring 1-positions and 3 A compound in which the relative configuration of the position is trans {(1R) -trans isomer} or an isomer mixture rich in (1R) -trans isomer is preferable.

In the present invention, C1-C6 represented by R ¹
Examples of the alkyl group include a methyl group, ethyl group and propyl group, and examples of the C3-C6 alkenyl group include an allyl group, 1-methyl-2-propenyl group and 3-
Examples thereof include a butenyl group, examples of the C3-C6 alkynyl group include a propargyl group, and examples of the C2-C6 haloalkyl group include a 2,2,2-trifluoroethyl group.

The compound of the present invention can be produced, for example, by the following (Production Method 1) to (Production Method 3).

(Manufacturing Method 1) Formula (2) (In the formula, R ¹ and R ² have the same meanings as described above.) And 4-methoxymethyl-2,
Method of reacting with 3,5,6-tetrafluorobenzyl alcohol The reaction is usually carried out in the presence of a condensing agent or an acid catalyst, usually in a solvent. Examples of the condensing agent used in the reaction include dicyclohexylcarbodiimide and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride.
Examples of the acid catalyst include inorganic acids such as sulfuric acid and organic acids such as paratoluenesulfonic acid and methanesulfonic acid. In this reaction, a solvent inert to the reaction can be used, and specific examples thereof include hydrocarbons such as toluene and hexane, ethers such as diethyl ether and tetrahydrofuran, dichloromethane, 1,2-dichloroethane and the like. Examples include halogenated hydrocarbons and mixtures thereof. The reaction time is usually from instant to 72 hours. The reaction temperature is usually in the range of -20 to 100 ° C.
4-methoxymethyl-2,3,5,6 used in the reaction
The tetrafluorobenzyl alcohol can achieve the purpose by 1 mol with respect to 1 mol of the carboxylic acid compound represented by the formula (2), but can usually be changed in the range of 0.5 to 1.5 mol. 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 compound represented by the formula (2),
It can be changed depending on the reaction situation. When the reaction is carried out in the presence of an acid catalyst, the acid catalyst used in the reaction can be used in any amount depending on the reaction situation.
After completion of the reaction, the compound of the present invention can be isolated by subjecting the reaction mixture to an organic solvent extraction and then subjecting it to a conventional post-treatment operation such as concentration. The isolated compound of the present invention can be further purified by chromatography, distillation or the like, if necessary.

A method of reacting a reactive derivative of a carboxylic acid compound represented by the formula (2) (acid halide, acid anhydride, etc.) with 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol. The reaction is usually performed in a solvent in the presence of a base. Examples of the base used in the reaction include triethylamine, pyridine, N, N-
Organic bases such as diethylaniline, 4-dimethylaminopyridine, diisopropylethylamine and the like can be mentioned. In this reaction, a solvent inert to the reaction can be used. Specifically, for example, hydrocarbons such as toluene and hexane, ethers such as diethyl ether and tetrahydrofuran,
Examples include halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, and mixed solvents thereof. The reaction time is usually from instant to 72 hours. The reaction temperature is usually in the range of -20 to 100 ° C.
4-methoxymethyl-2,3,5,6 used in the reaction
The tetrafluorobenzyl alcohol can achieve the purpose by 1 mol with respect to 1 mol of the reactive derivative of the carboxylic acid compound represented by the formula (2), but can be changed depending on the reaction situation. The base used in the reaction is the reactive derivative 1 of the carboxylic acid represented by the formula (2).
The purpose can be achieved with 1 mol per mol, but it can be changed depending on the reaction situation. After completion of the reaction, the compound of the present invention can be isolated by subjecting the reaction mixture to an organic solvent extraction and then subjecting it to a conventional post-treatment operation such as concentration. The isolated compound of the present invention can be further purified by chromatography, distillation or the like, if necessary.

(Production Example 3) Formula (3) 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl 3-formyl-2,2-dimethylcyclopropanecarboxylate represented by the formula (4) (In the formula, Ph represents a phenyl group, and R ¹ and R ² have the same meanings as described above.) A method of reacting with a phosphorane compound represented by the above. The reaction is usually performed in a solvent. Examples of the solvent used in the reaction include hydrocarbons such as toluene and hexane, ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane, sulfoxides such as dimethyl sulfoxide, water, and mixed solvents thereof. It can be selected depending on the phosphorane compound represented by the formula (4) to be used. The reaction time is usually from instant to 72 hours. The reaction temperature range is
It is usually in the range of -80 to 100 ° C. The amount of the phosphorane compound of the formula (4) used in the reaction can be 1 mol per 1 mol of the aldehyde compound represented by the formula (3), but it can be changed depending on the reaction situation. Examples of the phosphorane compound represented by the formula (4) used in the reaction include a corresponding phosphonium salt compound and a base (lithium diisopropylamide, sodium hexamethyldisilazide, butyl lithium, sodium methoxide, potassium carbonate, etc.). Is appropriately selected according to the type of the) and is prepared at the time of use by reacting with. After completion of the reaction, the reaction mixture is poured into water, extracted with an organic solvent, and then subjected to usual post-treatments such as concentration, and if necessary, further purification operations such as chromatography and distillation are performed. Invention compounds can be obtained.

4-Methoxymethyl-2,3,5,6-tetrafluorobenzyl 3-formyl-2,2-dimethylcyclopropanecarboxylate has the formula (5) 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate shown by ozonolysis or osmium tetroxide -It can be produced by reacting with sodium metaperiodate.

4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol is described in JP-A-57-12.
It is a compound described in Japanese Patent No. 3146, and can be produced by the method described in that publication. Also, equation (2)
Some of the carboxylic acid compounds represented by and their reactive derivatives can be produced, for example, by the method described in JP-A No. 54-130537. further,
The ester compound represented by the formula (5) is disclosed in, for example, JP-A-20
The compounds described in JP-A No. 01-11022 can be produced by the method described in that publication.

The pests to be controlled by the compound of the present invention include, for example, arthropods such as insects and mites, and linear animals such as nematodes. Specific examples include the following.

[0014] Lepidoptera pest insects such as the larvae of the larvae of the genus Lepidoptera, Plutella xylostella, Nostoc commune, etc. Agrotis spp., Helicoverpa pest (Hel)
icoverpa spp.), pests of the genus Heliotis (Heliothis sp
p.), diamondback moth, Ichon disseri, moth, Koga, etc.

Diptera pests such as Culex pipiens, Culex pipiens and similar mosquitoes, Aedes aegypti such as Aedes aegypti and Aedes albopictus, Anopheles mosquito such as Aedes albopictus, Chironomidae, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Flies Onion fly and other fruit flies, fruit flies, fruit flies, fruit flies, fleas,
Flies, gnats, flies, midges, etc.

Pteroptera insects German cockroaches, Black cockroaches, American cockroaches, Black cockroaches, German cockroaches, etc. Heptoptera insect pests Ants, wasps, hornets, etc. Hipoptera such as turnip bees, etc. Infectious worms, cat fleas, human fleas, etc.

Lice pests Human lice, lice, head lice, lice, etc. Isoptera pests Yamato termites, house termites, etc.

[0018] Planthoppers such as Hemiptera pests, the brown planthopper, the brown planthopper, the green leafhopper, the leafhoppers such as the leafhopper, the aphid, the stink bugs, the whiteflies, the scale insects, the ground beetle, the psyllid and the like.

Corn root worms such as Coleoptera pest insects Pleurotus cerevisiae, Pseudococcidae symphysis, Western corn root worm, Southern corn root worm, etc., Chafer beetles such as Rhododendron buoy, Hime beetle, Weevil Weevil, Weevil Weevil, Weevil Weevil, Weevil Weevil, Weevil Weevil
White beetle such as white rice beetle, Kodokustomodoki, rice beetle beetle, leaf beetle beetle, beetle such as sea urchin beetle, syring beetle, Epilachna spp.
Flat beetle, long-tailed beetle, long-horned beetle, red-tailed beetle, etc.

Pests of the order Thysanoptera, Thrips palmatum, Thrips thrips, Thrips thrips, etc. Orthoptera insect pests, grasshoppers, etc.

Tick mites such as Dermatophagoides farinae, Dermatophagoides farinae, Acarina such as Plutella xylostella, Mite, etc. Spider mites such as Nami mites, Kanzawa mites, mandarin mites, apple mites, and ticks such as Phytophthora infestans

The pest control agent of the present invention may be the compound of the present invention itself, but it is usually prepared by formulating the compound of the present invention. The preparation includes, for example, oils, emulsions, wettable powders, flowables (suspending agents in water, emulsions in water, etc.), powders, granules, aerosols, heat vaporizing agents (insecticides, electric insecticide mats, liquid absorbents). Core-type heating evaporation insecticide, etc.), heating smoke agent (self-burning smoke agent, chemical reaction type smoke agent, porous ceramic plate smoke agent, etc.), non-heat evaporation agent (resin evaporation agent,
Impregnated paper vaporizer, etc.), Fume agent (focking, etc.), ULV
Examples include medicines 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, a liquid carrier, a gaseous carrier, a bait, etc., and if necessary, a surfactant and other auxiliaries for formulation are added and processed. (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 formulations usually contain 0.001 to 95% by weight of the compound of the present invention, depending on the formulation form.

Examples of carriers used for formulation include solid carriers {clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talc, ceramics, other inorganic minerals ( Sericite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, montmorillonite, etc.), chemical fertilizers (ammonium sulfate, phosphorus ammonium, ammonium nitrate, urea, ammonium ammonium salt, etc.)}, liquid carriers {water, alcohols (methanol, ethanol) Etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, phenylxylylethane, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.) ),
Esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide) Etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, vegetable oils (soybean oil, cottonseed oil, etc.)} and gaseous carriers {freon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, Carbon dioxide, etc.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers, polyoxyethylene compounds of alkyl aryl ethers, polyethylene glycol ethers, and polyhydric alcohols. Examples thereof include esters and sugar alcohol derivatives.

Other auxiliaries for formulation include sticking agents,
Dispersants and stabilizers, such as casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, synthetic water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone), polyacrylic acid, etc. BHT (2,6-di-t-butyl-4-methylphenol) and BHA (2-t-
Butyl-4-methoxyphenol and 3-t-butyl-4
-Mixture with methoxyphenol).

Examples of the base material for insecticidal incense include a mixture of vegetable powder such as wood powder and meal powder and a binder such as tab powder, starch and glutein.

Examples of the base material for the electric insecticidal mat include those obtained by hardening cotton linter into a plate shape and those obtained by hardening a filible of a mixture of cotton linter and pulp into a plate shape.

Examples of the base material of the self-combustion type smoke agent include, for example, nitrates, nitrites, guanidine salts, potassium chlorate, nitrocellulose, ethylcellulose, combustion heat generating agents such as wood powder, alkali metal salts and alkaline earth metals. Pyrolysis stimulants such as salts, dichromates and chromates, oxygen supply agents such as potassium nitrate, combustion-supporting agents such as melamine and wheat starch,
Examples include extenders such as diatomaceous earth and binders such as synthetic pastes.

Examples of the base material of the chemical reaction type smoke agent include alkali metal sulfides, polysulfides, hydrosulfides, hydrous salts, heat generating agents such as calcium oxide, carbonaceous substances, iron carbide,
Examples thereof include catalyst agents such as activated clay, azodicarbonamide, benzenesulfonyl hydrazide, organic foaming agents such as dinitropentamethylenetetramine, polystyrene and polyurethane, and fillers such as natural fiber pieces and synthetic fiber pieces.

Examples of the base material of the non-heated transpiration agent include thermoplastic resin and paper (filter paper, Japanese paper, etc.).

Examples of the base material of the poison bait include bait ingredients such as cereal flour, vegetable oil, sugar and crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguacetic acid, preservatives such as dehydroacetic acid, and capsicum. Examples include an accidental food intake preventive agent for children and pets such as powder, and a pest-attracting flavor such as cheese flavor, onion flavor, and peanut oil.

The pest control method of the present invention is usually carried out by applying the pest control agent of the present invention to a pest or a habitat of a pest. The pest control agent of the present invention is applied, for example, by the following method, and can be appropriately selected according to the dosage form of the preparation, the place of use, and the like. (1) A method of treating the pesticide as it is to pests or habitats of pests. (2) A method in which the production is diluted with a solvent such as water and then sprayed on the pest or a habitat of the pest. In this case, usually, an emulsion, a wettable powder, a flowable agent, a microcapsule preparation or the like having a concentration of the compound of the present invention of 0.1 to 10,000 is used.
Dilute to ppm. (3) A method of heating the preparation in a habitat of pests or pests to volatilize the active ingredient. 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 type of formulation, application time, application site, application method, pest type, damage situation and the like.

Pest control agents containing the compound of the present invention include other insecticides, nematicides, soil pest control agents, fungicides,
It can be mixed or used together with a herbicide, a plant growth regulator, a repellent, a synergist, a fertilizer, and a soil conditioner.

Examples of active ingredients of such insecticides and acaricides include fenitrothion, fenthion, diazinon, chlorpyrifos, acephate, methidethione, disulfoton, DDVP, sulprophos, cyanophos, dioxabenzophos, dimethoate, fentoate, malathion, trichlorfon. , Azinphos-methyl,
Organophosphorus compounds such as monocrotophos and ethion,

Carbamate compounds such as BPMC, benfuracarb, propoxur, carbosulfan, carbaryl, mesomil, ethiophenecarb, aldicarb, oxamyl and phenothiocarb,

Etofenprox, fenvalerate, esfenvalerate, fenpropatorin, cypermethrin, permethrin, cyhalothrin, deltamethrin, cycloprothrin, fluvalinate, bifenthrin, 2-methyl-2- (4-bromodifluoromethoxyphenyl) Propyl (3-phenoxybenzyl) ether, tralomethrin, silafluophene, d-phenothrin, cifenotrin, d-resmethrin, acrinathrin, cyfluthrin, tefluthrin, transfluthrin, tetramethrin, arethrin, prarethrin, enpentrin, imiprothrin, d-flamethrin, 5
A pyrethroid compound such as-(2-propynyl) furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate,

N-cyanoamidine derivatives such as nitroimidazolidine derivatives, N-cyano-N'-methyl-N '-(6-chloro-3-pyridylmethyl) acetamidine,
Chlorinated hydrocarbon compounds such as endosulfan, γ-BHC, 1,1-bis (chlorophenyl) -2,2,2-trichloroethanol, benzoylphenylurea compounds such as chlorfluazuron, teflubenzuron and flufenoxuron, Phenylpyrazole compounds, methoxadiazone, bromopropylate, tetradiphone, quinomethionate, pyridaben, fenpyroximate, diafenthiuron, debufenpyrad, polynactin complex (tetranactin, dinactin, trinactin), pyrimidifen, milbemectin, abamectin, iva-mectin and azadirachtin. To be

As the active ingredient of the repellent, for example, 3,
Plant essential oils such as 4-calanediol, N, N-diethyl-m-toluamide, 1-methylpropyl 2- (2-hydroxyethyl) -1-piperidinecarboxylate, p-menthane-3,8-diol and hissop oil. Can be given.

Examples of the active ingredient of the synergist include bis- (2,3,3,3-tetrachloropropyl) ether (S-421) and N- (2-ethylhexyl) bicyclo.
[2.2.1] Hept-5-ene-2,3-dicarboximide (MGK-264) and 5-[[2- (2-butoxyethoxy) ethoxy] methyl] -6-propyl-
1,3-benzodioxole (piperonyl butoxide)
Can be given

[0040]

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

First, production examples of the compound of the present invention will be shown.

Production Example 1 0.96 g of cyclopentyltriphenylphosphonium bromide in 10 ml of tetrahydrofuran under a nitrogen atmosphere.
2.3 ml of a tetrahydrofuran solution (1 mol / l) of sodium hexamethyldisilazide was added thereto, and the mixture was stirred at room temperature for 30 minutes. Here, 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl
0.81 g of 3-formyl-2,2-dimethylcyclopropanecarboxylate (produced according to the method described in Reference Production Example described later) was added, and the mixture was stirred at room temperature for 8 hours. Then, the reaction mixture was poured into about 20 ml of 1% hydrochloric acid and extracted twice with 100 ml of ethyl acetate. The organic layers were combined, washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain the formula (6). Compound represented by (hereinafter, referred to as present invention compound 1)
0.59 g was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.
15 (s, 3H), 1.26 (s, 3H), 1.40
(D, 1H), 1.64 (m, 4H), 2.02 (m,
1H), 2.24 (m, 4H), 3.40 (s, 3)
H), 4.59 (s, 2H), 5.00 (m, 1H),
5.22 (s, 2H)

Production Example 2 Formula (7) was prepared in the same manner as in Production Example 1 except that cyclopropyltriphenylphosphonium bromide was used instead of cyclopentyltriphenylphosphonium bromide. A compound represented by (hereinafter, referred to as present compound 2) was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.
03 (m, 4H), 1.17 (s, 3H), 1.28
(S, 3H), 1.64 (d, 1H), 2.24 (m,
1H), 3.40 (s, 3H), 4.59 (s, 2)
H), 5.23 (s, 2H), 5.55 (m, 1H)

Production Example 3 Formula (8) was obtained in the same manner as in Production Example 1 except that cyclobutyltriphenylphosphonium bromide was used instead of cyclopentyltriphenylphosphonium bromide. A compound represented by (hereinafter, referred to as present compound 3) was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.
14 (s, 3H), 1.27 (s, 3H), 1.44
(D, 1H), 1.96 (m, 2H + 1H), 2.70
(M, 4H), 3.40 (s, 3H), 4.59 (s,
2H), 4.81 (m, 1H), 5.25 (s, 2H)

Production Example 4 Formula (9) was obtained in the same manner as in Production Example 1 except that 1-ethylpropyltriphenylphosphonium bromide was used instead of cyclopentyltriphenylphosphonium bromide. A compound represented by (hereinafter, referred to as present compound 4) was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 0.
95 (t, 6H), 1.12 (s, 3H), 1.26
(S, 3H), 1.40 (m, 1H), 2.06 (m,
1H), 2.10 (m, 4H), 3.40 (s, 3)
H), 4.59 (s, 2H), 4.89 (m, 1H),
5.22 (s, 2H)

Production Example 5 Formula (10) was prepared in the same manner as in Production Example 1 except that 1-methylpropyltriphenylphosphonium bromide was used instead of cyclopentyltriphenylphosphonium bromide. A compound represented by (hereinafter, referred to as present compound 5) was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.
00 (t, 3H), 1.12 (s, 3H), 1.26
(S, 3H), 1.39 (m, 1H), 1.69 (m,
3H), 2.01 (m, 1H), 2.10 (m, 2)
H), 3.40 (s, 3H), 4.59 (s, 2H),
4.85 (m, 1H), 5.22 (s, 2H)

Production Example 6 Formula (11) was prepared in the same manner as in Production Example 1 except that 3-butenyltriphenylphosphonium bromide was used instead of cyclopentyltriphenylphosphonium bromide. A compound represented by (hereinafter, referred to as present compound 6) was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.
14 (s, 3H), 1.27 (s, 3H), 1.48
(M, 1H), 2.15 (m, 1H), 2.88 (m,
2H), 3.40 (s, 3H), 4.59 (s, 2)
H), 4.90 to 5.30 (m, 2H + 1H), 5.2
2 (s, 2H), 5.53 (m, 1H), 5.82
(M, 1H)

Production Example 7 Formula (12) was prepared in the same manner as in Production Example 1 except that 3-butynyltriphenylphosphonium bromide was used instead of cyclopentyltriphenylphosphonium bromide. A compound represented by (hereinafter, referred to as present compound 7) was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.
15 (s, 3H), 1.25 (s, 3H), 1.50
(M, 1H), 1.98 (m, 1H), 2.14 (m,
1H), 3.02 (m, 2H), 3.40 (s, 3)
H), 4.58 (s, 2H), 5.20 (m, 1H),
5.23 (s, 2H), 5.57 (m, 1H)

Production Example 8 3,3,3 in 10 ml of 0.5% water-containing 1,4-dioxane
Suspension of 1.53 g of trifluoropropyltriphenylphosphonium iodide, 0.44 g of potassium carbonate and 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl 3-formyl-2,2-dimethylcyclopropanecarboxy 1.0 g of rate (produced according to the method described in Reference Production Example described later) was added, and the mixture was stirred at 95 ° C. for 4 hours. Then, the reaction mixture was allowed to cool to room temperature, poured into water, and extracted twice with 100 ml of ethyl acetate. The organic layers were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain the formula (13). Compound represented by (hereinafter, referred to as present compound 8)
0.95 g was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.
16 (s, 3H), 1.28 (s, 3H), 1.57
(M, 1H), 2.09 (m, 1H), 2.93 (m,
2H), 3.40 (s, 3H), 4.58 (s, 2
H), 5.24 (s, 2H), 5.46 (m, 1H),
5.51 (m, 1H)

Next, 4-methoxymethyl-2,3,5,6
-A method for producing tetrafluorobenzyl 3-formyl-2,2-dimethylcyclopropanecarboxylate will be described as a reference production example.

Reference Production Example 4-methoxymethyl was added to 10 ml of tetrahydrofuran.
1.0 g of 2,3,5,6-tetrafluorobenzyl alcohol and 0.42 g of pyridine were dissolved and the mixture was cooled to 3 with ice.
-(2-Methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylic acid chloride {stereoisomeric ratio
(1R) -trans form: (1R) -cis form: (1S)-
Trans form: (1S) -cis form = 93.9: 2.5:
3.5: 0.1} 0.9 g was added, and the mixture was further stirred at room temperature for 8 hours. After that, the reaction solution was poured into about 50 ml of ice water,
It was extracted twice with 80 ml of ethyl acetate. The organic layers were combined, washed with saturated brine and dried over anhydrous sodium sulfate,
It was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography to give 4-methoxymethyl-2,3,3.
5,6-Tetrafluorobenzyl 3- (2-methyl-
1.4 g of 1-propenyl) -2,2-dimethylcyclopropanecarboxylate was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.
13 (s, 3H), 1.26 (s, 3H), 1.38
(D, 1H), 1.69 (brs, 6H), 2.10
(Dd, 1H), 3.40 (s, 3H), 4.59
(S, 2H), 4.87 (d, 1H), 5.24 (d
d, 2H)

In a mixed solvent of 25 ml of tetrahydrofuran and 150 ml of 1,4-dioxane, 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl 3- (2
-Methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate (15.4 g) was dissolved, osmium tetroxide (1.0 g) was added at room temperature, and sodium metaperiodate (24.0 g) was dissolved in water (50 ml). After adding the solution, the mixture was heated under reflux for 2 hours. Then add about 2 parts of water to the reaction mixture.
It was poured into 00 ml and extracted twice with 200 ml of ethyl acetate. The organic layers are combined and a 1% aqueous sodium thiosulfate solution is added.
The extract was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue is subjected to silica gel column chromatography to give 4-methoxymethyl- of the formula (3).
10.4 g of 2,3,5,6-tetrafluorobenzyl 3-formyl-2,2-dimethylcyclopropanecarboxylate was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 1.
30 (s, 3H), 1.36 (s, 3H), 2.47
(M, 2H), 3.41 (s, 3H), 4.59 (s,
2H), 5.26 (s, 2H), 9.59 (s, 1H)

Formulation examples are shown below. In addition, a part shows a weight part.

Formulation Example 1 20 parts of the compounds of the present invention 1 to 8 are dissolved in 65 parts of xylene, 15 parts of Solpol 3005X (registered trademark of Toho Kagaku) is added, and well mixed with stirring to obtain an emulsion.

Formulation Example 2 40 parts of the compound of the present invention was added to solpol 3005X5
32 parts of Carplex # 80 (synthetic hydrous silicon oxide, Shionogi Pharmaceutical Co., Ltd.) and 23 parts of 300 mesh diatomaceous earth are added and mixed with stirring with a juice mixer to obtain a wettable powder.

Formulation Example 3 10 parts of the compound of the present invention 1 to 8 parts, 10 parts of phenylxylylethane and 0.5 part of Sumidule L-75 (tolylene diisocyanate, manufactured by Sumitomo Bayer Urethane Co., Ltd.) were mixed, and then gum arabic was added. Add to 20 parts of 10% aqueous solution,
Stir with a homomixer to obtain an emulsion having an average particle size of 20 μm. Next, 2 parts of ethylene glycol was added thereto, and the mixture was further stirred in a warm bath at 60 ° C. for 24 hours to obtain a microcapsule slurry. On the other hand, xanthan gum 0.2
Part, and 1.0 part of Veegum 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 4 After mixing 10 parts of the compound of the present invention 1-8 with phenylxylylethane 10% of polyethylene glycol
Add to 20 parts of the aqueous solution and stir with a homomixer to obtain an emulsion solution having an average particle size of 3 μm. On the other hand, 0.2 part of xanthan gum and 1.0 part of Veegum R (aluminum magnesium silicate, manufactured by Sanyo Kasei) were deionized water 5
Disperse into 8.8 parts 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 5 Carplex # 80 (synthetic hydrous silicon oxide fine powder, Shionogi registered trademark) 3 parts, P
0.3 parts AP (mixture of monoisopropyl phosphate and diisopropyl phosphate) and 91.7 parts talc (300 mesh) are added, and the mixture is stirred and mixed with a juice mixer to obtain a dust.

Formulation Example 6 0.1 parts of the compounds of the present invention are dissolved in 5 parts of dichloromethane and mixed with 94.9 parts of deodorized kerosene to obtain an oil solution.

Formulation Example 7 1 part of the compounds 1 to 8 of the present invention, 5 parts of dichloromethane and 34 parts of deodorant kerosene were mixed and dissolved, and the mixture was filled in an aerosol container,
After the valve portion is attached, 60 parts of propellant (liquefied petroleum gas) is charged under pressure through the valve portion to obtain an oil-based aerosol.

Formulation Example 8 Compounds of the present invention 1 to 8 0.6 parts, xylene 5 parts, deodorizing kerosene 3.4 parts and Atmos 300 (emulsifier, registered trademark of Atlas Chemical Co.) 1 part were mixed and dissolved, and water 50 Parts and an aerosol container, and 40 parts of propellant (liquefied petroleum gas) is pressure-filled through the valve part to obtain an aqueous aerosol.

Formulation Example 9 0.3 g of the compounds 1 to 8 of the present invention are dissolved in 20 ml of acetone, and a base material for incense sticks (a mixture of tab powder: meal powder: wood powder = 4: 3: 3) 99. After uniformly stirring and mixing with 7 g, 100 ml of water was added, and the mixture thoroughly kneaded was molded and dried to obtain an insecticidal incense stick.

Formulation Example 10 Acetone was added to 0.8 g of the compounds 1 to 8 of the present invention and 0.4 g of piperonyl butoxide to dissolve them, and a total of 10
Set to ml. 0.5 ml of this solution is 2.5 cm x 1.5
cm, and a thickness of 0.3 cm for a base for an electric insecticide mat (a fibril of a mixture of cotton linter and pulp is hardened into a plate) is uniformly impregnated to obtain an electric insecticide matting agent.

Formulation Example 11 3 parts of the compounds of the present invention 1 to 8 were dissolved in 97 parts of deodorizing kerosene to obtain a liquid agent, which was placed in a vinyl chloride container and the upper portion of which was heated by a heater (inorganic powder). The body is hardened with a binder and sintered) is inserted to obtain parts used for the liquid-wicking heating evaporation device.

Formulation Example 12 100 mg of the present compounds 1 to 8 are 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 smoking agent.

Formulation Example 13 100 μg of the compounds of the present invention 1 to 8 are dissolved in an appropriate amount of acetone, uniformly applied on a filter paper of 2 cm × 2 cm and 0.3 mm in thickness, and then acetone is air-dried to obtain a room temperature volatilizer. .

Formulation Example 14 Acetone solutions of the compounds 1 to 8 of the present invention are impregnated into a filter paper so that the concentration of the compound of the present invention is 1 g per 1 m ² , and acetone is air-dried to obtain a mite-proof sheet.

Next, it will be shown by test examples that the compound of the present invention is effective as an active ingredient of a pest controlling agent.

Test Example Compounds 1 to 8 of the present invention were diluted to 0.1% with acetone, and the diluted solution was applied to the chest back of adult female Culex pipiens mosquito so that the amount of active ingredient was 0.3 μg / head, and water was added. I left it while feeding. After 24 hours, the number of surviving, anguished, and dead insects was investigated to determine the rate of bitter insects (1 group, 10 animals, 2 replications). As a result, all of the compounds of the present invention showed a rate of bitter insects of 100%.

INDUSTRIAL APPLICABILITY The compound of the present invention has excellent pest control activity and is useful as an active ingredient of a pest control agent.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H006 AA01 AA03 AB02 BJ20 BJ50                       BM30 BM71 BP10                 4H011 AC01 AC04 BA01 BB15 BC18                       BC19 BC20 BC22 DA02 DA06                       DA07 DA10 DA15 DA16 DA21                       DD04 DD05 DD06 DE05 DE07                       DE16 DH03 DH10

Claims (3)

[Claims] 1. A formula (1) [Wherein, R ¹ and R ² are (A), (B) or (C). (A) R ¹ represents a hydrogen atom or a C1-C6 alkyl group, and R ² represents a C3-C6 alkenyl group, a C3-C6 alkynyl group or a C2-C6 haloalkyl group. (B) R ¹ represents a methyl group or an ethyl group, and R ² represents an ethyl group or a propyl group. ; (C) R ¹
And R ² are bonded at the terminal to represent an ethylene group, a trimethylene group, or a tetramethylene group. ] The ester compound shown by these. 2. A pest control agent comprising the ester compound according to claim 1 as an active ingredient. 3. A method for controlling pests, which comprises applying the ester compound according to claim 1 to pests or habitats of pests.