JP2000229914A - Ester compound - Google Patents

Abstract

(57) [Problem] To provide an ester compound having practical pest control effect. SOLUTION: Formula 1 4-methoxy-2,3,5,6-tetrafluorobenzyl 3- (2,2-difluorovinyl)-
A pest control agent comprising 2,2-dimethylcyclopropanecarboxylate and an active ingredient containing the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ester compound and a pesticidal composition containing the same as an active ingredient.

[0002]

2. Description of the Related Art It has been known that certain ester compounds have insecticidal and acaricidal activity (JP-A-56-97251). However, it is not always sufficient as an active ingredient of a pesticide in terms of practical control effect. Under such circumstances, the present invention provides a compound having excellent pest control activity.

[0003]

Means for Solving the Problems The present inventors have conducted intensive studies to find a compound having an excellent pest control effect, and as a result, an ester compound represented by the following formula 2 has excellent pest control activity. Have been found, leading to the present invention. That is, the present invention provides

Embedded image 4-methoxy-2,3,5,6-tetrafluorobenzyl 3- (2,2-difluorovinyl)-
Provided are 2,2-dimethylcyclopropanecarboxylate (hereinafter, referred to as the present compound) and a pesticidal composition containing the same as an active ingredient.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds of the present invention include four types of stereoisomers (1R) -trans, (1S) -trans, which are related to two asymmetric carbon atoms on a cyclopropane ring.
(1R) -cis form and (1S) -cis form. (1R) and (1S) mean the position and absolute configuration in the cyclopropane ring, and trans and cis mean the relative configuration of the 1- and 3-position substituents on the cyclopropane ring. Are present, each of which and mixtures thereof are included in the present invention.

The compound of the present invention has, for example, the following formula:

Embedded image And an alcohol compound represented by the formula

Embedded image And a reactive derivative thereof (for example, an acid halide, an acid anhydride, etc.). The reaction is usually
The reaction is performed in a solvent in the presence of a condensing agent or a base. Examples of the condensing agent include dicyclohexylcarbodiimide (DCC) and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (WS
C) and the like. As the base, for example, triethylamine, pyridine, N, N-diethylaniline, 4-
Organic bases such as dimethylaminopyridine or diisopropylethylamine are exemplified. Examples of the solvent include hydrocarbons such as benzene, toluene and hexane or ethers such as diethyl ether and tetrahydrofuran;
Examples thereof include halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane. The range of the reaction time is
Usually 5 minutes to 72 hours. The reaction temperature range is usually from -20 ° C to the boiling point of the solvent used for the reaction or 100 ° C.
And the range of -5 ° C to the boiling point of the solvent used in the reaction or 100 ° C is preferred. The molar ratio of the alcohol compound represented by the formula (3) to the carboxylic acid compound represented by the formula (4) or a reactive derivative thereof can be arbitrarily set, but it is preferable to carry out the reaction in an equimolar or close ratio. The condensing agent or base can be used in an equimolar amount to an excess amount, and preferably in an equimolar to 5 mole ratio, relative to 1 mole of the alcohol compound represented by the formula (3). The compound of the present invention can be obtained by pouring the reaction solution after completion of the reaction into water and performing post-treatment operations such as extraction with an organic solvent and concentration. The compound of the present invention can be purified by operations such as chromatography and distillation.

The alcohol compound represented by the formula 3 is
For example, according to the method described in JP-A-56-97251, the carboxylic acid represented by Chemical formula 4 can be used, for example, in JP-A-57-14299.
It can be manufactured according to the method described in 3.

The pests against which the compound of the present invention exerts control effects include, for example, the following. Lepidopteran pests Japanese bats, such as Japanese scabbard moth, Kobu nomeiga, Noshime kokuga, Spodoptera litura, Armyworm, Spodoptera litura, etc .; Agrotis spp., Helicoverpa spp.
overpa spp.), Heliothis pest (Heliothis spp.),
Diptera pests, such as Conger moth, Ichimon disseri, Iga, Koiga, Noshimekokuga, etc. , Flies, flies, flies, onions and other flies, fruit flies, fruit flies, flies, flies, black flies, sand flies, brassicae, etc. Hymenoptera pests Ants, hornets, wasps, and wasps such as wasps, etc. Wing pests Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides, Dermatophagoides and Dermatophagoids. , House spider mites, red spider mite, Kanzawa spider mite, mandarin spider mite, apple spider mite, spider mite such as red mite, ticks such as spider mite Hemiptera insect pests , Whiteflies, scale insects, hornworms, psyllids, etc. Coleopteran pests Tan corn rootworm, corn root worms such as Southern corn rootworm, cupreous chafer, beetles such as rufocuprea, maize weevil, rice water weevil, boll weevil, weevils such as adzuki bean weevil,
Dermatophagoid beetles, such as Pterodactyla beetle and Scarab beetle, Beetle beetles such as rice beetle, rice beetle, beetle flea beetle, leaf beetle such as beetle, epilumna spp. Pterodactyla etc. Panoptera pests Thrips palmi, Thrips palmi, Thrips etc. Orthoptera pests Kera, grasshopper, etc.

[0008] In the present invention, the pesticidal agent is intended for insecticide and repelling pests. When the compound of the present invention is used as an active ingredient of a pesticidal agent, it is usually necessary to mix it with a solid carrier, liquid carrier, gaseous carrier, bait, or impregnate it into a substrate such as a mosquito coil or mat. If surfactants and other formulation auxiliaries are added,
Oils, emulsions, wettable powders, flowables such as suspensions in water and emulsions in water, granules, powders, aerosols, tranquilizers such as mosquito coils, electric mosquito mats, and liquid electric mosquito coils, self-heating Combustion-type smokers, chemical-reaction-type smokers, heated smokers such as porous ceramic plate smokers, non-heated vaporizers such as resin vaporizers and impregnated paper vaporizers, fogging agents such as fogging, ULV agents, It is used as a poison bait. The compound of the present invention is particularly useful as an active ingredient of a non-heated transpiration agent such as a heated transpiration agent such as the above-mentioned mosquito coil, electric mosquito trap and liquid electric mosquito trap, and a resin transpiration agent or an impregnated paper transpiration agent. In these preparations, the compound of the present invention is usually used as an active ingredient in an amount of 0.001 to 95% by weight.
contains. Examples of the solid carrier used in such formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasamikure, acid clay, etc.), talcs, ceramics, and other inorganic minerals (sericite). , Quartz, activated carbon, calcium carbonate, hydrated silica, etc.) and the like, and liquid carriers such as water, alcohols (methanol,
Ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methyl naphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, gas 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, soybean oil, vegetable oils such as cottonseed oil and the like. Examples of the gaseous carrier, that is, propellant, for example, Freon gas, Examples include butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbon dioxide gas. As the surfactant, for example, an alkyl sulfate salt,
Alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like. . Examples of pharmaceutical auxiliaries such as fixatives and dispersants include casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, saccharides, synthetic water-soluble polymers (Polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.). Examples of the stabilizer include PA
P (acidic isopropyl phosphate), BHT (2,6-di-
tert-butyl-4-methylphenol), BHA
(2-tert-butyl-4-methoxyphenol and 3
-Tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof, and the like.

As the base material of the mosquito coil, for example, wood flour,
Examples of the mixture include a mixture of a raw plant powder such as meal powder and a binder such as tab powder, starch and glutein. Examples of the base material of the electric mosquito collecting mat include a plate obtained by hardening fibrils of cotton linter or a mixture of cotton linter and pulp. Examples of the base material of the self-combustion type smoke agent include combustion exothermic agents such as nitrates, nitrites, guanidine salts, potassium chlorate, nitrocellulose, ethylcellulose, and wood flour; alkali metal salts; alkaline earth metals Thermal decomposition stimulants such as salts, dichromates and chromates,
Examples include oxygen supply agents such as potassium nitrate, flame retardants such as melamine and wheat starch, extenders such as diatomaceous earth, and binders such as synthetic paste. As the base material of the chemical reaction type smoke agent, for example, exothermic agents such as sulfides of alkali metals, polysulfides, hydrosulfides, hydrated salts, calcium oxide, carbonaceous substances,
Examples include catalysts such as iron carbide and activated clay, organic blowing agents such as azodicarbonamide, benzenesulfonylhydrazide, dinitrosopentamethylenetetramine, polystyrene, and polyurethane, and fillers such as natural fiber pieces and synthetic fiber pieces. Examples of the base material of the non-heated evaporant include a thermoplastic resin, filter paper, Japanese paper, and the like. Examples of the bait bait include bait ingredients such as cereal flour, vegetable oil, sugar and crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaseletic acid, preservatives such as dehydroacetic acid, and pepper powder. And the like, and chewing agents such as cheese flavor, onion flavor, peanut oil and the like. Formulations of flowables (suspension in water or emulsions in water) generally contain 1-75% of the compound of the invention in 0.5-1%.
5% of a dispersant, 0.1 to 10% of a suspension aid (for example, a protective colloid or a compound imparting thixotropic properties), 0
In water containing 10% to 10% of appropriate adjuvants (eg antifoaming agents, rust inhibitors, stabilizers, spreading agents, penetration aids, antifreezing agents, antibacterial agents, fungicides, etc.) Obtained by dispersing. Instead of water, an oil in which the compound of the present invention hardly dissolves may be used as a suspension in oil. As the protective colloid, for example, gelatin, casein, gums, cellulose ether, polyvinyl alcohol and the like are used. Examples of the compound imparting thixotropic properties include bentonite, aluminum magnesium silicate, xanthan gum, polyacrylic acid and the like.

The preparation thus obtained is used as it is or after dilution with water or the like. Also other pesticides,
It can be mixed or used in combination with acaricides, repellents, synergists and the like. Such insecticides, acaricides, for example,
Fenitrothion [O, O-dimethyl O- (3-methyl-4-nitrophenyl) phosphorothioate], fenthion [O, O-dimethyl O- (3-methyl-4-
(Methylthio) phenyl) phosphorothioate], diazinon [O, O-diethyl-O-2-isopropyl-
6-methylpyrimidin-4-yl phosphorothioe-
G), chloropyrifos [O, O-diethyl-O-3,
5,6-trichloro-2-pyridyl phosphorothioe-
Acetoate [O, S-dimethylacetylphosphoramide thioate], methidathion [S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3] -Ylmethyl O, O-dimethyl phosphorodithioate], disulfotone [O, O-diethyl S
-2-ethylthioethyl phosphorodithioate], DD
VP [2,2-dichlorovinyldimethylphospho-
G), sulprophos [O-ethyl O-4- (methylthio) phenyl S-propyl phosphorodithioate],
Cyanophos [O-4-cyanophenyl O, O-dimethyl phosphorothioate], dioxabenzophos [2-methoxy-4H-1,3,2-benzodioxaphosphorin-2-sulfide], dimethoate [O, O-dimethyl-S- (N-methylcarbamoylmethyl) dithiophosphate], fentoate [ethyl 2-dimethoxyphosphinothioylthio (phenyl) acetate], malathion [diethyl (dimethoxyphosphino) Thioylthio) succinate], trichlorfon [dimethyl 2,2
2,2-trichloro-1-hydroxyethylphosphone-
G], azinphosmethyl [S-3,4-dihydro-4-
Oxo-1,2,3-benzotriazin-3-ylmethyl O, O-dimethylphosphorodithioate], monocrotophos [dimethyl (E) -1-methyl-2- (methylcarbamoyl) vinyl phosphate], Ethion [O,
Organic phosphorus compounds such as O, O ', O'-tetraethyl S, S'-methylenebis (phosphorodithioate)], B
PMC (2-sec-butylphenylmethylcarbamine
G), benfracarb [ethyl N- [2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N-isopropyl-
β-alaninate], propoxur [2-isopropoxyphenyl N-methylcarbamate], carbosulfan [2,3-dihydro-2,2-dimethyl-7-benzo [b] furanyl N-dibutylamino Thio-N-methylcarbamate], carbaryl [1-naphthyl-N-methylcarbamate], mesomil [S-methyl-N-
[(Methylcarbamoyl) oxy] thioacetimide
G], Ethiophenecarb [2- (ethylthiomethyl)
Phenylmethylcarbamate], aldicarb [2-methyl-2- (methylthio) propionaldehyde O-
Methylcarbamoyl oxime], oxamyl [N, N-
Dimethyl-2-methylcarbamoyloxyimino-2-
(Methylthio) acetamide], phenothiocarb [S-
Carbamate compounds such as 4-phenoxybutyl) -N, N-dimethylthiocarbamate;

Ethofenprox [2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether], fenvalerate [(RS) -α-
Cyano-3-phenoxybenzyl (RS) -2- (4
-Chlorophenyl) -3-methylbutyrate], esfenvalerate [(S) -α-cyano-3-phenoxybenzyl (S) -2- (4-chlorophenyl) -3-
Methylbutyrate], fenpropatrin [(RS)-
α-cyano-3-phenoxybenzyl 2,2,3,3
-Tetramethylcyclopropanecarboxylate], cypermethrin [(RS) -α-cyano-3-phenoxybenzyl (1RS) -cis, trans-3- (2,2
-Dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzyl (1RS) -cis, trans-3- (2,2-
Dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], cyhalothrin [(RS) -α-cyano-3-phenoxybenzyl (Z)-(1RS) -cis
-3- (2-chloro-3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate], deltamethrin [(S) -α-cyano-3-phenoxybenzyl (1R) -cis-3 (2,
2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate], cycloprothrin [(RS)-
α-cyano-3-phenoxybenzyl (RS) -2,2
-Dichloro-1- (4-ethoxyphenyl) cyclopropanecarboxylate], fluvalinate (α-cyano-3-phenoxybenzyl N- (2-chloro-α, α,
α-trifluoro-p-tolyl) -D-barynate),
Bifenthrin (2-methylbiphenyl-3-ylmethyl) (Z)-(1RS) -cis-3- (2-chloro-
3,3,3-trifluoroprop-1-enyl) -2,
2-dimethylcyclopropanecarboxylate, 2-methyl-2- (4-bromodifluoromethoxyphenyl)
Propyl (3-phenoxybenzyl) ether, tralomethrin [(1R-cis) 3-{(1RS) (1,2,2
2,2-tetrabromoethyl) {-2,2-dimethylcyclopropanecarboxylic acid (S) -α-cyano-3-phenoxybenzyl ester], silafluofen [4-ethoxyphenyl} 3- (4-fluoro-3- Phenoxyphenyl) propyl @ dimethylsilane], d-phenothrin [3-phenoxybenzyl (1R-cis, trans) -chrysanthemate], cyphenothrin [(RS)
-Α-cyano-3-phenoxybenzyl (1R-cis, trans) -chrysanthemate], d-resmethrin [5-benzyl-3-furylmethyl (1R-cis, trans) -chrysanthemate], acrinasulin [( S) -α-cyano-3-phenoxybenzyl (1
R-cis (Z))-(2,2-dimethyl-3- {3-oxo-3- (1,1,1,3,3,3-hexafluoropropyloxy) propenyl} cyclopropanecarboxylate ], Cyfluthrin [(RS) -α-cyano-4
-Fluoro-3-phenoxybenzyl 3- (2,2-
Dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], tefluthrin [2,3,5,6-tetrafluoro-4-methylbenzyl (1RS-cis (Z))-3- (2-chloro- 3,3,3-trifluoroprop-1-enyl) -2,2-dimethylcyclopropanecarboxylate], transfluthrin [2,
3,5,6-tetrafluorobenzyl (1R-trans) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], tetramethrin [3,4,5,6-tetrahydro Phthalimidomethyl (1RS) -cis, trans-chrysanthemate],
Allethrin [(RS) -3-allyl-2-methyl-4-
Oxocyclopent-2-enyl (1RS) -cis, trans-chrysanthemate], prarethrin [(S)-
2-methyl-4-oxo-3- (2-propynyl) cyclopent-2-enyl (1R) -cis, trans-chrysanthemate], empentrin [(RS) -1-ethynyl-2-methyl-2-pentenyl (1R) -cis,
Trans-chrysanthemate], imiprothrine [2,
5-dioxo-3- (prop-2-ynyl) imidazolidin-1-ylmethyl (1R) -cis, trans-2,
2-dimethyl-3- (2-methylprop-1-enyl)
Cyclopropanecarboxylate], d-framethrin [5- (2-propynyl) furfuryl (1R) -cis,
Trans-chrysanthemate], pyrethroid compounds such as 5- (2-propynyl) furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate;

Nitroimidazolidines, N-cyanoamidine derivatives such as N-cyano-N'-methyl-N '-(6-chloro-3-pyridylmethyl) acetamidine, endosulfan [6,7,8,9,10 , 10-
Hexachloro-1,5,5a, 6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine oxide], γ-BHC (1,2,3,4,
5,6-hexachlorocyclohexane], 1,1-bis (chlorophenyl) -2,2,2-trichloroethanol-
Chlorinated hydrocarbon compounds such as chlorofluazuron [1
-(3,5-dichloro-4- (3-chloro-5-trifluoromethylpyridin-2-yloxy) phenyl)-
3- (2,6-difluorobenzoyl) urea], teflubenzuron [1- (3,5-dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea], flufenoxuron [1 − (4- (2-
Benzoylphenylurea-based compounds such as chloro-4-trifluoromethylphenoxy) -2-fluorophenyl] -3- (2,6-difluorobenzoyl) urea]
Diafenthiuron [N- (2,6-diisopropyl-
Thiourea derivatives such as 4-phenoxyphenyl) -N'-tert-butylcarbodiimide;
Methoxadiazone [5-methoxy-3-
(2-methoxyphenyl) -1,3,4-oxadiazol-2- (3H) -one], bromopropylate [isopropyl 4,4'-dibromobenzylate], tetradiphone [4-chlorophenyl 2, 4,5-trichlorophenylsulfone], quinomethionate [S, S-6
-Methylquinoxaline-2,3-diyldithiocarbonate], pyridaben [2-tert-butyl-5- (4
-Tert-butylbenzylthio) -4-chloropyridazin-3 (2H) -one], fenpyroximate [t
tert-butyl (E) -4-[(1,3-dimethyl-5
-Phenoxypyrazol-4-yl) methyleneaminooxymethyl] benzoate], debufenpyrad [N-
4-tert-butylbenzyl) -4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide],
Polynactin complex (tetranactin, dinactin, trinactin), pyrimidifene [5-chloro-
N- [2- {4- (2-ethoxyethyl) -2,3-dimethylphenoxy} ethyl] -6-ethylpyrimidine-
4-amine, milbemectin, abamectin, iva-mectin, azadirachtin [AZAD] and the like. Examples of repellents include 3,4-caranediol, N,
N-diethyl-m-toluamide, 1-methylpropyl
Vegetable essential oils such as 2- (2-hydroxyethyl) -1-piperidine carboxylate, p-menthane-3,8-diol, hyssop oil and the like can be mentioned. 3,3-tetrachloropropyl) ether (S-421), N- (2-ethylhexyl) bicyclo [2,2,1] hept-5-ene-2,3
Dicarboximide, (MGK-264), α- [2
-(2-butoxyethoxy) ethoxy] -4,5-methylenedioxy-2-propyltoluene (piperonylbutoxide) and the like.

When the compound of the present invention is used as an active ingredient in a household pest control or animal pest control agent, the emulsion, wettable powder, flowable and the like are usually 0.1 to 10,000 pp in water.
m, and applied as oils, azole, fumigants, fumigations, transpirants, aerosols, ULVs, poison baits, resin preparations and the like. These application concentrations differ depending on the type of preparation, application time, application place, application method, type of pest, degree of damage, and the like, and can be increased or decreased without being affected by the above range. The compound of the present invention exerts a high pest control effect (insect and repellent effect) by volatilizing it under heated or non-heated conditions. Therefore, the compound of the present invention is particularly effective as a pest control agent for household epidemic control and clothing pest control. Useful as an ingredient.

[0014]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Production Examples, Preparation 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 (1R) -trans-3- (2,2-difluorovinyl) was added to a mixed solution of 602 mg of 4-methoxy-2,3,5,6-tetrafluorobenzyl alcohol, 484 mg of pyridine and 20 ml of toluene under ice-cooling. ) After addition of 580 mg of -2,2-dimethylcyclopropanecarboxylic acid chloride, stirring was continued at room temperature for 8 hours. The reaction solution was poured into about 100 ml of ice water, and extracted twice with 100 ml of ethyl acetate. The combined ethyl acetate layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.
A crude oil was obtained. The crude oil was subjected to silica gel column chromatography to give 4-methoxy-2,3,5,6-
Tetrafluorobenzyl (1R) -trans-3-
(2,2-difluorovinyl) -2,2-dimethylcyclopropanecarboxylate (Compound 1 of the present invention) 770
mg (69% yield). ¹ H-NMR (CDCl ₃ , TMS internal standard) δ value (pp
m): 1.15 (s, 3H), 1.28 (s, 3H), 1.45
(d, 1H), 2.02 (dd, 1H), 4.01 (ddd,
1H), 4.10 (s, 3H), 5.19 (d, 2H)

Examples of the compound of the present invention are shown below together with the compound numbers. Compound of the present invention 1: 4-methoxy-2,3,5,6-tetrafluorobenzyl (1R) -trans-3- (2,
2-difluorovinyl) -2,2-dimethylcyclopropanecarboxylate Compound of the present invention 2: 4-methoxy-2,3,5,6-tetrafluorobenzyl (1RS) -cis, trans-3
-(2,2-Difluorovinyl) -2,2-dimethylcyclopropanecarboxylate Compound 3 of the present invention: 4-methoxy-2,3,5,6-tetrafluorobenzyl (1R) -cis-3- (2, 2-
Difluorovinyl) -2,2-dimethylcyclopropanecarboxylate

Next, preparation examples will be shown. Parts represent parts by weight. Formulation Example 1 Emulsion 20 parts of each of Compounds 1 to 3 of the present invention are dissolved in 65 parts of xylene, 15 parts of an emulsifier Solpol 3005X (trade name of Toho Chemical Co., Ltd.) is added, and the mixture is thoroughly stirred and mixed to give a 20% emulsion of each. Get. Formulation Example 2 wettable powder Each of the compounds 1 to 3 of the present invention has 40 parts of sorbol 3005
5 parts of X (as described above) were added and mixed well, and 32 parts of Carplex # 80 (trade name of Shionogi & Co., Ltd., synthetic hydrous silicon oxide fine powder) and 23 parts of 300 mesh diatomaceous earth were added. Stir and mix to obtain each 40% wettable powder. Formulation Example 3 Granules 1.5 parts of each of Compounds 1 to 3 of the present invention and AGSORB
98.5 parts of LVM-MS24 / 48 (a calcined product of montmorillonite manufactured by OIL DRI, a granular carrier having a particle size of 24 to 48 mesh) are added and mixed well to obtain 1.5% granules of each.

Formulation Example 4 Microcapsules 10 parts of each of the present compounds 1 to 3, 10 parts of phenylxylylethane and 0.5 part of Sumidur L-75 (Tolylene diisocyanate manufactured by Sumitomo Bayer Urethane Co.) Is added to 20 parts of a 10% aqueous solution of gum arabic and stirred with a homomixer to obtain an emulsion having an average particle size of 20 μm. Next, 2 parts of ethylene glycol is added thereto, and the mixture is further reacted in a hot bath at 60 ° C. for 24 hours to obtain a microcapsule slurry. On the other hand, 0.2 part of Xanthan gum and 1.0 part of Bee gum R (aluminum magnesium silicate manufactured by Sanyo Chemical) are dispersed in 56.3 parts of ion-exchanged water to obtain a thickener solution. 42.5 parts of the above microcapsule slurries and 57.5 parts of the thickener solution are mixed to obtain 10% microcapsules of each. Formulation Example 5 Flowable agent After mixing 10 parts of each of Compounds 1 to 3 of the present invention and 10 parts of phenylxylylethane, 1 part of polyethylene glycol was added.
0% aqueous solution in 20 parts and stirred with a homomixer.
An emulsion having an average particle size of 3 μm is obtained. On the other hand, 0.2 part of Xanthan gum and 1.0 part of Beegum R (aluminum magnesium silicate manufactured by Sanyo Chemical Co.) were replaced with 58.8 ion-exchanged water.
To obtain a thickener solution. Emulsion 40 above
Parts and 60 parts of the thickener solution are mixed to obtain each 10% flowable. Formulation Example 6 Dust 5 parts each of Compounds 1 to 3 of the present invention were used in Carplex # 80.
3 parts (as described above), 0.3 part of PAP and 91.7 parts of 300 mesh talc are added and mixed by stirring with a Juice mixer to obtain 5% powder of each.

Formulation Example 7 Oil 0.1 part of each of the present compounds 1 to 3 is dissolved in dichloromethane 5
And then mixed with 94.9 parts of deodorized kerosene to obtain 0.1% oil in each case. Formulation Example 8 Oily Azole 1 part of each of the present compounds 1 to 3, 5 parts of dichloromethane and 34 parts of deodorized kerosene are mixed and dissolved, filled in an aerosol container, a valve part is attached, and then the valve part is passed. 60 parts of a propellant (liquefied petroleum gas) is charged under pressure to obtain each oily aerosol. Formulation Example 9 Aqueous Aerosol 0.6 parts of each of the present compounds 1 to 3, 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of an emulsifier {Atomos 300 (trade name of Atlas Chemical Co.)} were mixed and dissolved. And 50 parts of pure water are charged into an aerosol container, a valve is attached, and 40 parts of a propellant (liquefied petroleum gas) is charged under pressure through the valve to obtain each aqueous aerosol. .

Formulation Example 10 Mosquito coil: 0.3 g of each of the present compounds 1 to 3 is mixed with 20 ml of acetone.
Mosquito coil (tab flour: lees flour: wood flour 4:
After mixing uniformly with 99.7 g), 120 ml of water was added, and the mixture was sufficiently kneaded and molded and dried to obtain each mosquito coil. Formulation Example 11 Electric Mosquito Mat Acetone is added to 0.8 g of each of Compounds 1 to 3 of the present invention and 0.4 g of piperonyl butoxide to make 10 ml with a total. 0.5 ml of this solution is 2.5 cm x 1.
A 5 cm, 0.3 cm thick substrate for an electric mat (a fibril of a mixture of cotton linter and pulp solidified in a plate shape) is uniformly impregnated to obtain each electric mosquito repellent. Formulation Example 12 Liquid Electric Mosquito Removal 3 parts of each of Compounds 1 to 3 of the present invention are dissolved in 97 parts of deodorized kerosene, placed in a container made of vinyl chloride, and an upper part which can be heated with a heater (inorganic liquid). Each of the liquid electric mosquitoes is obtained by inserting a powder obtained by solidifying and sintering the powder with a binder.

Formulation Example 13 Heating Smoke Agent 100 mg of each of the present compounds 1 to 3 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. Obtain a smoke agent. Formulation Example 14 Room Temperature Volatilizer 100 μg of each of Compounds 1 to 3 of the present invention is dissolved in an appropriate amount of acetone, and uniformly applied to a filter paper having a size of 2 cm × 2 cm and a thickness of 0.3 mm. Obtain a transpiration agent. Formulation Example 15 Room-Temperature Volatilizer 100 mg of each of the present compounds 1 to 3 is dissolved in an appropriate amount of acetone, and the solution is uniformly applied to a filter paper having a size of 20 cm × 50 cm and a thickness of 0.3 mm. Obtain a transpiration agent. Formulation Example 16 Anti-mite sheet Each of Compounds 1 to 3 of the present invention is dropped and impregnated into filter paper at 1 g per 1 m ² , and acetone is air-dried to obtain each anti-mite sheet.

Next, Test Examples show that the compound of the present invention is useful as an active ingredient of a practical pest control agent. Test Example 1 normal temperature volatilization Insecticidal Test polyethylene cup against webbing clothes moth by (bottom diameter 10 cm, diameter opening 12.5 cm, height 9.5cm, volume 950cm ³⁾ 2cm × 2cm wool muslin cloth and webbing clothes moth in old at the bottom of the 10 larvae were placed in the filter paper, and a predetermined amount of the compound shown in Table 1 was treated from the lid with a filter paper (2
(cm × 2 cm). After leaving it at a temperature of 25 ° C. for one week, it was opened, and the mortality of trophozoites was determined. Further, the degree of damage to the wool muslin cloth was examined. The criteria for determining the degree of damage were +++: markedly damaged ++: slightly damaged +: slightly damaged ±: slightly damaged-: no damage (2 repetitions). Table 1 shows the results.

[Table 1] The control compound A is represented by the formula 5 described in JP-A-56-97251.

Embedded image And the control compound B is disclosed in
Formula 6 produced according to the method described in JP-A-97251.

Embedded image It is a compound shown by these. In Test Example 1, in the test using Compound 1 of the present invention, immediately after the start of the test and 1
At the time of observation after one week, no discoloration or off-odor of the drug-treated filter paper was observed.

Test Example 2 Knockdown test for Culex pipiens at room temperature volatilization 0.64 ml of a 0.002% (w / v) acetone diluted solution of the test compound was dropped into an aluminum dish (diameter at the bottom 7 cm), and the acetone was air-dried. . Ten female adults of Culex pipiens pallens were released into a polyethylene cup (diameter 9 cm, height 4.5 cm), and a 16-mesh nylon net was placed on the top to prevent the insects from directly touching the drug-treated surface. Invert the cup, place on the above aluminum pan, and incubate at 25 ° C for 60
After standing for a minute, the knock-down insect rate of the test insects was investigated. As a result, Compound 1 of the present invention showed a knockdown insect rate of 100%. In contrast, the control compound A, the control compound B, and no treatment (no active ingredient) showed a knockdown insect rate of 0%.

Test Example 3 Discoloration test for brass (alloy of copper and zinc) 3.3 mg of Compound 1 of the present invention was dissolved in acetone, the acetone solution was applied to a 2 cm × 1.5 cm filter paper, and air-dried. A drug-treated filter paper was prepared. Brass powder-treated filter paper [Brass powder (Cu / Zn = 76-78 / 22-24)
mg / cm ^{2 at} a rate of 5.5 mm in diameter on one side of a filter paper], folded in two with the brass powder-treated side inward, and the above-mentioned drug-treated filter paper was sandwiched in this, and clipped. Was sealed by heat sealing in an aluminum laminate bag, and kept in a thermostat at 60 ° C. for 24 hours. Thereafter, the package was opened, and the discoloration and odor of the filter paper treated with brass powder and the filter paper treated with a chemical were examined. As a result, no odor or discoloration was observed in both the brass powder-treated filter paper and the chemical-treated filter paper.

[0024]

The compound of the present invention is excellent in pest control effect and is extremely useful as an active ingredient of a pest control agent, particularly a pest control agent for home epidemic control or clothing insect control.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA01 AB02 AC48 BA51 BB11 BB12 BB15 BC10 BC19 BJ50 BM30 BM71 BP30 BT22 FC22 FE74 4H011 AC01 AC02 AC03 AC04 AC05 AC06 BB15 DA02 DA06 DA07 DA12 DA15 DA16 DA21 DE05 DE06 DE07 DE07

Claims (7)

[Claims] [Claim 1] Formula 1 4-methoxy-2,3,5,6-tetrafluorobenzyl 3- (2,2-difluorovinyl)-
2,2-dimethylcyclopropane carboxylate. 2. The compound according to claim 1, wherein the substituents at the 1- and 3-positions in the cyclopropane ring are at the trans position. 3. The compound according to claim 1, wherein the 1-position in the cyclopropane ring has an R configuration. 4. A pesticidal composition comprising the compound according to claim 1 as an active ingredient. 5. The pesticidal composition according to claim 4, wherein the pesticidal composition is for household epidemics. 6. The pesticidal composition according to claim 4, wherein the pesticidal composition is a heat transpiration agent for household epidemics. 7. The pesticidal composition according to claim 4, wherein the pesticidal composition is used for clothing insect repellent.