JP2000063343A - Ester compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound having excellent pestcontrolling activity, especially, insecticidal and miticidal activities, and having quick effects and safety. SOLUTION: This ester compound is shown by formula I [R is H, a (halogenated) 1-3C alkyl or (halogenated) allyl or propargyl; X is H, a halogen, a (halogenated)1-3C alkyl, (halogenated) 2-3C alkenyl or the like], e.g. (1R)- trans-3-[(Z)-methoxyiminomethyl]-2,2-dimethylcyclopropanecarboxylic acid (2,3,5,6- tetrafluoro-4-methylphenyl)methyl ester. The compound of formula I is obtained e.g. by reacting a carboxylic acid of formula II or a reactive derivative thereof with an alcoholic compound of formula III or a reactive derivative thereof. When the compound of formula I is to be used as an active ingredient of a pest-controlling agent, its amount to be applied is pref. 5-500 g per 10 a.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ester compound and a pest control agent containing the same as an active ingredient.

[0002]

2. Description of the Related Art Conventionally, some kind of 2,2-dimethyl-3-
It is known that (oxyiminomethyl) cyclopropanecarboxylic acid benzyl esters have insecticidal and acaricidal activity (see JP-A-56-7750).

[0003]

However, it cannot be said that the insecticidal and acaricidal activities of these compounds are practically sufficient.

[0004]

Means for Solving the Problems As a result of intensive studies to find a compound having an excellent pest control effect, the present inventors have found that an ester compound represented by the following general formula (2) is excellent in pest control. The inventors have found that they have activity, immediate effect and safety, and have completed the present invention. That is, the present invention is
General formula

[Chemical 2] [In the formula, R represents a hydrogen atom, a C1 to C3 alkyl group optionally substituted with a halogen atom, an allyl group optionally substituted with a halogen atom or a propargyl group optionally substituted with a halogen atom, X is a hydrogen atom, a halogen atom, or C1 to be optionally substituted with a halogen atom.
C3 alkyl group, C2 to C3 alkenyl group optionally substituted with halogen atom, C2 to C3 alkynyl group optionally substituted with halogen atom, C1 to C3 alkoxy group optionally substituted with halogen atom, halogen An optionally substituted C1-C3 alkylthio group,
Or, (C1 optionally substituted with a halogen atom
C3 alkoxy) represents a methyl group. ] The ester compound shown by these (henceforth compound of this invention) and the pest control agent containing it as an active ingredient are provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom,
Examples of the C1-C3 alkyl group which may be substituted with a halogen atom include a methyl group, an ethyl group and a trifluoromethyl group, and examples of the allyl group which may be substituted with a halogen atom include an allyl group. Examples of the propargyl group which may be substituted with a halogen atom include a propargyl group and the like, and examples of the C2-C3 alkenyl group which may be substituted with a halogen atom include an allyl group and the like, which are substituted with a halogen atom. May be C2-C
Examples of the 3 alkynyl group include a propargyl group and the like, and the C1 to C3 alkoxy group which may be substituted with a halogen atom include a methoxy group, a trifluoromethoxy group and the like, which may be substituted with a halogen atom. Examples of the preferable C1-C3 alkylthio group include a methylthio group and the like ((C which may be substituted with a halogen atom)
A methoxymethyl group etc. are mentioned as a 1-C3 alkoxy) methyl group.

The compound of the present invention can be produced, for example, by the following method. (Production Method A) General Formula 3

[Chemical 3] [In the formula, R represents the same meaning as described above. ] The carboxylic acid compound or its reactive derivative represented by

[Chemical 4] [In the formula, X represents the same meaning as described above. ] The manufacturing method by making it react with the alcohol compound shown by these, or its reactive derivative. The reaction is usually carried out in an organic solvent, optionally in the presence of a reaction aid while optionally removing by-products from the reaction system. The reaction time is usually from 5 minutes to 72 hours, and the reaction temperature is usually from -80 ° C to the boiling point of the solvent used in the reaction or 20
The range is up to 0 ° C. The reactive derivative of the carboxylic acid compound represented by the general formula 3 is an acid halide,
Examples thereof include acid anhydrides and C1-C4 alkyl esters. Examples of the reactive derivative of the alcohol compound represented by the general formula 4 include halides, sulfonic acid esters, quaternary ammonium salts and the like. General formula 3
The molar ratio of the carboxylic acid compound represented by or the reactive derivative thereof to the alcohol compound represented by the general formula 4 or the reactive derivative thereof can be set arbitrarily, but is preferably equimolar or a ratio close thereto. Examples of the reaction aid include tertiary amines such as triethylamine, 4-dimethylaminopyridine and diisopropylethylamine, nitrogen-containing aromatic compounds such as pyridine, sodium methoxide,
Organic bases such as alkali metal alkoxides such as potassium tert-butoxide, inorganic bases such as sodium hydroxide, potassium carbonate and sodium hydride, protonic acids such as p-toluenesulfonic acid and sulfuric acid, titanium (IV) phenoxide and the like. Examples thereof include Lewis acids, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, and reagents of diethylazodicarboxylate and triphenylphosphine. These reaction auxiliaries are appropriately selected depending on the kind of the carboxylic acid compound represented by the general formula 3 or the reactive derivative thereof or the alcohol compound represented by the general formula 4 or the reactive derivative used in the reaction, and The amount used is appropriately selected depending on the reaction form. Examples of the organic solvent include hydrocarbons such as benzene, toluene and hexane, ethers such as diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, amides such as dimethylformamide, and acetone. Examples thereof include ketones, organic sulfur such as dimethyl sulfoxide, and the like, and a mixture thereof. The compound of the present invention can be obtained by subjecting the reaction solution after completion of the reaction to conventional post-treatment operations such as extraction with an organic solvent and concentration. The compound is chromatographed, distilled,
It can also be purified by an operation such as recrystallization. The carboxylic acid compound represented by the general formula 3 or its reactive derivative is described in J. Chem. Soc. Perkin Trans. 1 2470 (1970).
Alternatively, it can be produced according to the method described in JP-A No. 54-160343, and the alcohol compound represented by the general formula 4 or its reactive derivative can be prepared by
3-79845, JP-A-56-97251, JP-A-57-123146 or JP-A-61.
It can be manufactured according to the method described in JP-A-207361.

(Manufacturing Method B) General Formula 5

[Chemical 5] [In the formula, X represents the same meaning as described above. ] And an aldehyde compound represented by the general formula:

[Image Omitted] RONH ₂ [In the formula, R represents the same meaning as described above. ] The manufacturing method by making it react with the hydroxylamine compound shown by these, or its protonic acid salt. The reaction is usually carried out in a solvent, if necessary, in the presence of a reaction aid. The reaction time range is usually 5 minutes to 72 hours, and the reaction temperature range is usually from −80 ° C. to the boiling point of the solvent used in the reaction or 10
The range is up to 0 ° C. The amount of the reagent used in the reaction is usually 1 mol to an excess amount of the hydroxylamine compound represented by the general formula 6 or its protonic acid salt, relative to 1 mol of the aldehyde compound represented by the general formula 5.
The ratio is preferably 1 mol to 5 mol. Examples of the proton acid salt of the hydroxylamine compound include, for example, hydrochloride and sulfate. The reaction aid used as necessary includes tertiary amines such as triethylamine, 4-dimethylaminopyridine and diisopropylethylamine, nitrogen-containing aromatic compounds such as pyridine, alkali metal alkoxides such as sodium methoxide and sodium acetate and organic compounds. Examples thereof include organic bases such as acid salts, and inorganic bases such as sodium hydroxide and potassium carbonate. Examples of the solvent include hydrocarbons such as benzene, toluene and hexane, ethers such as diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, amides such as dimethylformamide, alcohols such as methanol. Kind,
Examples thereof include organic sulfurs such as dimethyl sulfoxide, organic acids such as acetic acid, water and the like, and mixtures thereof. The compound of the present invention can be obtained by subjecting the reaction solution after completion of the reaction to conventional post-treatment operations such as extraction with an organic solvent and concentration. The compound can also be purified by operations such as chromatography, distillation and recrystallization. The aldehyde compound represented by the general formula 5 is disclosed in JP-A-49-47531.
It can be manufactured according to the method described in the publication.

The compound of the present invention in which R is not a hydrogen atom can be produced from the compound of the present invention in which R is a hydrogen atom, for example, by the following method. (Production method C) The compound of the present invention in which R is a hydrogen atom and the general formula

[Image Omitted] R ¹ L [wherein R ¹ is C optionally substituted with a halogen atom]
1 to C3 represents an alkyl group, an allyl group optionally substituted with a halogen atom or a propargyl group optionally substituted with a halogen atom, L is a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, methanesulfonyl Oxy group, optionally substituted alkylsulfonyloxy group such as trifluoromethanesulfonyloxy group, optionally substituted arylsulfonyloxy group such as p-toluenesulfonyloxy group, substituted such as methoxysulfonyloxy group Represents a leaving group such as alkoxysulfonyloxy group, substituted ammonio group such as trimethylammonio group, and substituted iodonio group such as phenyliodonio group. ] The method of manufacturing by making it react with the compound shown by these. The reaction is usually carried out in an organic solvent, optionally in the presence of a reaction aid. The reaction time is usually 5 minutes to 72 hours, and the reaction temperature is usually -80 ° C to the boiling point of the solvent used in the reaction or 100 ° C. The amount of the reagent used in the reaction is usually 1 mol to an excess amount, preferably 1 mol to 5 mol, of the compound represented by the general formula 7 relative to 1 mol of the compound of the present invention in which R is a hydrogen atom. Is the ratio. Examples of the reaction aid used as necessary include tertiary amines such as triethylamine, 4-dimethylaminopyridine and diisopropylethylamine, nitrogen-containing aromatic compounds such as pyridine, and potassium ter.
Examples thereof include alkali metal alkoxides such as t-butoxide and silver trifluoromethanesulfonate, organic bases such as organic acid salts, and inorganic bases such as sodium hydroxide, potassium carbonate and sodium hydride. As an organic solvent,
Hydrocarbons such as benzene, toluene and hexane, ethers such as diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, amides such as dimethylformamide, alcohols such as methanol and ethanol, Examples thereof include ketones such as acetone, organic sulfurs such as dimethyl sulfoxide, and mixtures thereof. The compound of the present invention can be obtained by subjecting the reaction solution after completion of the reaction to conventional post-treatment operations such as extraction with an organic solvent and concentration. The compound can also be purified by operations such as chromatography, distillation and recrystallization.

The compounds of the present invention include optical isomers (R, S) based on asymmetric carbon and geometrical isomers (E,) based on double bond.
Z) and cyclopropane ring-based geometrical isomers (cis, trans), the present invention includes all optical isomers, geometrical isomers and mixtures thereof having pest control activity.

Examples of the carboxylic acid compound represented by the general formula 3 include the following compounds. 3-methoxyiminomethyl-2,2-dimethylcyclopropanecarboxylic acid 3-ethoxyiminomethyl-2,2-dimethylcyclopropanecarboxylic acid

Examples of the alcohol compound represented by the general formula 4 include the following compounds. (2,3,5,6-tetrafluorophenyl) methanol (2,3,4,5,6-pentafluorophenyl) methanol (2,3,5,6-tetrafluoro-4-methylphenyl) methanol (2 , 3,5,6-Tetrafluoro-4-methoxyphenyl) methanol

Examples of the aldehyde compound represented by the general formula 5 include the following compounds. 3-formyl-2,2-dimethylcyclopropanecarboxylic acid (2,3,4,5,6-pentafluorophenyl)
Methyl 3-formyl-2,2-dimethylcyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methylphenyl) methyl 3-formyl-2,2-dimethylcyclopropanecarboxylic acid (2,3,5 5,6-Tetrafluoro-4-methoxyphenyl) methyl

Examples of the hydroxylamine compound represented by the general formula 6 include the following compounds. Hydroxylamine O-methylhydroxylamine O-ethylhydroxylamine O-allylhydroxylamine As the compound represented by the general formula 7, for example, the following compounds can be mentioned. Methyl chloride Ethyl bromide Methyl iodide Methyl methanesulfonate p-Toluene sulfonate Methyl dimethyl sulfate

Examples of pests (harmful insects and harmful mites) in pests for which the compound of the present invention exerts a controlling effect include the following. Hemiptera pests: planthoppers such as the brown planthopper, the brown planthopper, the brown planthopper, the leafhopper, the leafhopper such as the leafhopper, the aphid, the stink bug, the whitefly, scale insects, the ground beetle,
Lepidopteran pests such as psyllids: Plutella xylostella, Plutella xylostella, Plutella xylostella, etc., Spodoptera litura, Spodoptera litura, Spodoptera litura, etc. , Helicoverpa spp., Helicoverpa spp., Heliotis spp.
iothis spp.), diamondback moth, Plutella xylostella, mosquito, mosquito, and other diptera pests: Culex pipiens such as Culex pipiens, Culex pipiens, Aedes mosquitoes such as Aedes aegypti, Aedes albopictus, etc. , Fly flies, flesh flies, sand flies, Hime flies, onion flies, etc., fruit flies, fruit flies, fruit flies, butterfly flies, flies, gnats, flies, fleas, etc. Coleoptera: Western corn rootworm, Southern corn root Corn root worms such as worms, scarab beetles such as stag beetles, scarab beetles, weevils, weevils, weevils, weevils, weevil and other weevils, white rice weevil, beetle bug Shi such, Inedorooimushi, Kisujinomihamushi, Chrysomelidae such as corn rootworm, beetles such, Epilachna genera such as the beetle, Epilachna vigintioctopunctata
(Epilachna spp.), Flat beetle, long-tailed beetle, long-horned beetle, stag beetle, blue-footed stag beetle, etc. Thysanoptera, Hana thrips, and other pests of the order Hymenoptera: ants, wasps, vespids,
Orthoptera such as turnips such as turnips: Pteridae such as kerato and grasshoppers: Pteridae such as human flea, cat flea, etc. Dermatophagoides farinae, Plutella xylostella mites, Plutella xylostella, etc. And ticks such as Haemaphysalis longicornis. The compounds of the present invention are also effective against harmful insects having resistance to existing insecticides and acaricides.

The pest control agent of the present invention is intended for killing pests and repelling pests. When the compound of the present invention is used as an active ingredient of a pest control agent, it is usually mixed with a solid carrier, a liquid carrier, a gaseous carrier, a bait, or impregnated into a substrate such as a mosquito coil or a mat, and if necessary, an interface. Addition of activators and other auxiliaries for formulation, oils, emulsions, wettable powders, flowable agents such as water suspensions / emulsions, granules, powders, aerosols, mosquito coils, electric mosquito repellent mats and no mats Etc., self-combustion type smoke agent / chemical reaction type smoke agent, heating smoke agent such as porous ceramic plate smoke agent, non-heat agent such as resin vaporizer / impregnated paper vaporizer, fogging, etc. It is used as a fog agent, ULV agent, poison bait, etc. In these formulations, the compound of the present invention is usually added as an active ingredient in a weight ratio of 0.001 to 9
Contains 5%.

Examples of solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talc, ceramics and other inorganic minerals (seri Site, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), chemical fertilizers (ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ammonium ammonium etc.), etc. For example, water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane) , Kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile) Isobutyronitrile), 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, and the gaseous carrier, that is, the propellant, for example, Freon gas, Examples thereof include butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas and the like. As the surfactant, for example, alkyl sulfate ester salt,
Examples thereof include alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylene compounds thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like. Examples of auxiliary agents for formulation such as sticking agents and dispersants include casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl chloride). Alcohol, polyvinylpyrrolidone, polyacrylic acid, etc.) and the like, and examples of the stabilizer include
PAP (isopropyl acid phosphate), BHT (2,6-
Di-tert-butyl-4-methylphenol), BH
A (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, surfactant, fatty acid or ester thereof and the like can be mentioned. As a base material for mosquito coil
For example, raw vegetable powder such as wood powder and meal powder, and tab powder and star powder.
Examples of the mixture include a mixture with a binder such as chi and glutein.
Examples of the base material of the electric mosquito repellent mat include those obtained by hardening fibrils of cotton linter or a mixture of cotton linter and pulp into a plate shape. Examples of the base material for self-burning smoke agents include nitrates, nitrites, guanidine salts, potassium chlorate, nitrocellulose, ethylcellulose, wood powder and other combustion heat-generating agents, alkali metal salts, alkaline earth metals. Pyrolysis stimulants such as salts, dichromates and chromates, oxygen supplying agents such as potassium nitrate, combustion-supporting agents such as melamine and wheat starch, extenders such as diatomaceous earth, binders such as synthetic pastes, etc. can give. Examples of the base material for chemical reaction type smoke agents include alkali metal sulfides, polysulfides, hydrosulfides, hydrous salts, heat generating agents such as calcium oxide, carbonaceous materials, iron carbide, activated clay and the like catalysts. Agent,
Examples thereof include organic foaming agents such as azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenetetramine, 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, filter paper, Japanese paper, and the like. Examples of base materials for poison baits include grain flour, vegetable oil,
Sugar, food ingredients such as crystalline cellulose, antioxidants such as dibutylhydroxytoluene, nordihydroguaseletic acid, preservatives such as dehydroacetic acid, anti-ingestion agents such as capsicum powder, cheese flavor, onion flavor, peanut oil, etc. And the like. Formulations of flowable agents (suspension in water or emulsions in water) generally include 1-75% compound, 0.5-15% dispersant, 0.1-10% suspension aid (eg, protective agent). Colloids and compounds that impart thixotropy), 0 to 10% of appropriate auxiliary agents (for example, defoaming agents, rust inhibitors, stabilizers, spreading agents, penetration aids, antifreezing agents, antibacterial agents, It is obtained by finely dispersing in water containing a fungicide etc.). It is also possible to use an oil in which the compound is hardly dissolved in place of water to prepare 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 that imparts thixotropic properties include bentonite, aluminum magnesium silicate, xanthan gum, polyacrylic acid, and the like.

The thus obtained preparation is used as it is or after diluted with water or the like. Also other pesticides,
It can also be mixed or used in combination with acaricide, nematicide, soil pest control agent, fungicide, herbicide, plant growth regulator, repellent, synergist, fertilizer and soil conditioner. Such insecticides,
Examples of nematicides, acaricides and soil pest control agents include fenitrothion [O, O-dimethyl O- (3-methyl-4-nitrophenyl) phosphorothioate] and fenthion [O, O-dimethyl O- ( 3-methyl-4-
(Methylthio) phenyl) phosphorothioate], diazinone [O, O-diethyl-O-2-isopropyl-
6-methylpyrimidin-4-yl phosphorothioate], chlorpyrifos [O, O-diethyl-O-3,
5,6-Trichloro-2-pyridylphosphorothioate], acephate [O, S-dimethylacetylphosphoramidothioate], methidathion [S-2,3-dihydro-5-methoxy-2-oxo-1,3,4- Thiadiazol-3-ylmethyl O, O-dimethyl phosphorodithioate], disulfoton [O, O-diethyl S-2
-Ethylthioethyl phosphorodithioate], dichlorophos [2,2-dichlorovinyl dimethyl phosphate], sulprophos [O-ethyl O-4- (methylthio) phenyl S-propyl phosphorodithioate], cyanophos [O-4- Cyanophenyl O, O-dimethyl phosphorothioate], dimethoate [O, O-dimethyl-S-methylcarbamoylmethyl phosphorodithioate], fentoate [ethyl 2-dimethoxyphosphinothioylthio (phenyl) acetate], malathion [diethyl ( Dimethoxyphosphinothioylthio) succinate], trichlorfon [dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate], azinephosmethyl [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,
O, O ′, O′-tetraethyl-S, S′-methylenebis (phosphorodithioate)] and other organic phosphorus compounds,
BPMC (2-sec-butylphenylmethyl carbamate], benfuracarb [ethyl N- {2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio} -N-isopropyl-β-alaninate] , Propoxur [2-isopropoxyphenyl methylcarbamate], carbosulfan [2,3-dihydro-2,2-dimethyl-7-benzo [b] furanyl N-dibutylaminothio-N-methylcarbamate], carbaryl [1]. -Naphthyl-N-methylcarbamate], Methomyl [S-methyl-N- (methylcarbamoyloxy) thioacetimidate], Ethiophencarb [2- (ethylthiomethyl) phenylmethylcarbamate], Aldicarb [2-methyl-2-]
(Methylthio) propionaldehyde O-methylcarbamoyl oxime], oxamyl [N, N-dimethyl-
Carbamate compounds such as 2-methylcarbamoyloxyimino-2- (methylthio) acetamide], phenothiocarb [S-4-phenoxybutyl-N, N-dimethylthiocarbamate], etofenprox [2-
(4-Ethoxyphenyl) -2-methyl-1- (3-phenoxybenzyl) oxypropane], fenvalerate [(RS) -α-cyano-3-phenoxybenzyl]
(RS) -2- (4-chlorophenyl) -3-methylbutyrate], esfenvalerate [(S) -α-cyano-3-phenoxybenzyl (S) -2- (4-chlorophenyl) -3-methyl Butyrate], phenpropatrine [(RS) -α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin [(RS) -α-cyano-3-phenoxy] Benzyl (1RS) -cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzyl (1RS) -cis, trans-3- (2,2 2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], cyhalothrin [(RS) -α-cyano-3] Phenoxybenzyl
(1RS, 3Z) -cis-3- (2-chloro-3,3,3
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-valinate], bifenthrin [2 -Methyl-3-phenylbenzyl (1RS, 3
Z) -cis-3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate], halfenprox [2-
(4-Bromodifluoromethoxyphenyl) -2-methyl-1- (3-phenoxybenzyl) oxypropane], tralomethrin [(S) -α-cyano-3-phenoxybenzyl (1R) -cis-3- (1, 2, 2,
2-tetrabromoethyl) -2,2-dimethylcyclopropanecarboxylate], silafluofene [(4-
Ethoxyphenyl)-{3- (4-fluoro-3-phenoxyphenyl) propyl} dimethylsilane], d-phenothrin [3-phenoxybenzyl (1R) -cis, trans-2,2-dimethyl-3- (2- Methyl-
1-propenyl) cyclopropanecarboxylate],
Ciphenothrin [(RS) -α-cyano-3-phenoxybenzyl (1R) -cis, trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate], d-resmethrin [ 5-benzyl-3-furylmethyl (1R) -cis, trans-
2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate], acrinathrin [(S) -α-cyano-3-phenoxybenzyl]
(1R, 3Z) -cis- (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, 3
Z) -cis-3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate], transfluthrin [2,
3,5,6-Tetrafluorobenzyl (1R) -trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], tetramethrin [3,4,5,6-tetrahydrophthalimidomethyl] (1RS) -cis, trans-2,2-dimethyl-3
-(2-methyl-1-propenyl) cyclopropanecarboxylate], allethrin [(RS) -2-methyl-]
4-oxo-3- (2-propenyl) -2-cyclopenten-1-yl (1RS) -cis, trans-2,2
-Dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate], pralethrin [(S)
-2-Methyl-4-oxo-3- (2-propynyl)-
2-Cyclopenten-1-yl (1R) -cis, trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate], empentrine [(RS) -1-ethynyl-] 2-Methyl-2-pentenyl (1R) -cis, trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate], imiprothrin [2,5-dioxo-3-] (2-Propinyl) imidazolidin-1-ylmethyl (1R) -cis, trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate], d-flamethrin [5- (2-
Propinyl) furfuryl (1R) -cis, trans-
2,2-Dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate], 5- (2-propynyl) furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate and other pyrethroids Compound, buprofezin [2-tert-butylimino-3]
-Isopropyl-5-phenyl-1,3,5-thiadiazin-4-one] and other thiadiazine derivatives, nitroimidazolidine derivatives, cartap [S, S '-(2-dimethylaminotrimethylene) bis (thiocarbamate)], thiocyclam [N, N-dimethyl-1,2,3
-Trithian-5-ylamine], bensultap [S, S′-2-dimethylaminotrimethylene di (benzenethiosulfonate)], and other nereistoxin derivatives, N-cyano-N′-methyl-N ′-( 6-chloro-
N-cyanoamidine derivatives such as 3-pyridylmethyl) acetamidine, endosulfan [6,7,8,9,1]
0,10-hexachloro-1,5,5a, 6,9,9a
-Hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide], γ-BHC
[1,2,3,4,5,6-hexachlorocyclohexane], dicoform [1,1-bis (4-chlorophenyl)]
Chlorinated hydrocarbon compounds such as -2,2,2-trichloroethanol], chlorfluazuron [1- {3,5-dichloro-4- (3-chloro-5-trifluoromethylpyridine-2- Iloxy) phenyl} -3- (2,6-difluorobenzoyl) urea], teflubenzuron [1
-(3,5-dichloro-2,4-difluorophenyl)
-3- (2,6-Difluorobenzoyl) urea], Flufenoxuron [1- {4- (2-chloro-4-trifluoromethylphenoxy) -2-fluorophenyl}
-3- (2,6-difluorobenzoyl) urea] and other benzoylphenylurea compounds, amitraz [N-
Formamidine derivatives such as methyl-bis (2,4-xyliminomethyl) amine], diafenthiuron [N-
(2,6-diisopropyl-4-phenoxyphenyl)
-N'-t-butylthiourea], etc.,
N-phenylpyrazole compound, methoxadiazone [5-methoxy-3- (2-methoxyphenyl) -1,
3,4-oxadiazol-2- (3H) -one], bromopropylate [isopropyl 4,4′-dibromobenzilate], tetradiphone [4-chlorophenyl
2,4,5-Trichlorophenyl sulfone], quinomethionate [S, S-6-methylquinoxaline-2,3-
Diyldithiocarbonate], Propargit [2-
(4-tert-Butylphenoxy) cyclohexylprop-2-ylsulfite], fenbutatin oxide [bis {tris (2-methyl-2-phenylpropyl) tin} oxide], hexithiazox [(4R
S, 5RS) -5- (4-chlorophenyl) -N-cyclohexyl-4-methyl-2-oxo-1,3-thiazolidine-3-carboxamide], clofentezine [3,6-bis (2-chlorophenyl)] -1, 2, 4,
5-tetrazine], pyridaben [2-tert-butyl-5- (4-tert-butylbenzylthio) -4-chloropyridazin-3 (2H) -one], fenpyroximate [tert-butyl (E) -4- [ (1,3-
Dimethyl-5-phenoxypyrazol-4-yl) methyleneamino-oxymethyl] benzoate], tebufenpyrad [N-4-tert-butylbenzyl) -4-
Chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide], polynactin complex [tetranactin, dinactin, trinactin], pyrimidifen [5-chloro-N- [2- {4- (2-ethoxyethyl) -2] , 3-Dimethylphenoxy} ethyl] -6-ethylpyrimidin-4-amine], milbemectin, abamectin, ivermectin, azadirachtin [AZA
D] and the like, and examples of the repellent include 3,4-caranediol, N, N-diethyl-m-toluamide, and 2
1-methylpropyl- (2-hydroxyethyl) -1-piperidinecarboxylic acid, p-menthane-3,8-diol, vegetable essential oils such as hissop oil, and the like can be mentioned. Examples of synergists include bis (2,2 3,3,3-Tetrachloropropyl) ether (S-421), N- (2-ethylhexyl) bicyclo [2,2,1] hept-5-ene-2,
3-dicarboximide (MGK-264), α- [2
Examples include-(2-butoxyethoxy) ethoxy] -4,5-methylenedioxy-2-propyltoluene (piperonyl butoxide).

When the compound of the present invention is used as an active ingredient of an agricultural pest control agent, its application amount is usually 5 to 500 g per 10 ares, and the emulsion, wettable powder, flowable agent, etc. are diluted with water before application. In this case, the application concentration is usually 0.1 to 1000 ppm, and granules, powders, resin preparations, etc. are applied as they are without any dilution. When it is used as an active ingredient of a household or epidemic prevention or animal pest control agent, emulsions, wettable powders, flowable agents, etc. are usually diluted with water to 0.1 to 10,000 ppm and applied.
Oil agent, aerosol, fumigant, fumigant, transpiration agent, fog agent,
ULV agents, poison baits, resin formulations, etc. are applied as they are. The application amount and application concentration depend on the kind of formulation, application time, application place, application method, type of pest, degree of damage and the like, and can be increased or decreased without regard to the above range.

[0019]

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. The numbers of the compounds of the present invention are shown in Tables 1 to 8 below.

Production Example 1 A mixture of (2,3,5,6-tetrafluoro-4-methylphenyl) methanol (1.78 g), pyridine (0.87 g) and tetrahydrofuran (20 ml) was cooled with ice (1R).
-Trans-2,2-dimethyl-3- (2-methyl-1)
-Propenyl) cyclopropanecarboxylic acid chloride 2.
06 g was added, and the mixture was stirred at room temperature for 8 hours. The reaction solution was poured into about 100 ml of ice water, and this was added to 100 ml of ethyl acetate to obtain 2 ml.
This was extracted twice, the organic layers were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 20/1) to give (1R) -trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid. (2, 3, 5, 6
-Tetrafluoro-4-methylphenyl) methyl 2.7
5 g (yield 87%) was obtained. (1R) -trans-2,
2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methylphenyl) methyl 1.27 g, methanol 20 ml, ethyl acetate 20 ml -78 ℃ the mixture
After cooling to 0 ° C., oxygen containing ozone was blown in under stirring until the liquid color of the reaction liquid changed to blue. Then, nitrogen gas was blown into the reaction solution to remove excess ozone, 5 ml of dimethyl sulfide was added, and the temperature was raised to room temperature. 1
After a day, the reaction solution was concentrated under reduced pressure, and acetone 2 was added to the residue.
0 ml, 2 ml of water and 0.2 g of p-toluenesulfonic acid monohydrate were added, and the mixture was left at room temperature for 2 hours. The reaction solution was poured into water, this was extracted with diethyl ether, the organic layer was dried over anhydrous sodium sulfate, and then concentrated under reduced pressure conditions.
The residue was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10/1), and (1
R) -trans-3-formyl-2,2-dimethyl-cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methylphenyl) methyl 0.98 g (yield 8
2%) was obtained. mp 43.2 ° C

O-methylhydroxylamine hydrochloride 0.
32 g, sodium hydroxide 0.16 g, methanol 10
The ml mixture was stirred for 1 hour. To this mixture (1R)
A solution of 0.56 g of (2,3,5,6-tetrafluoro-4-methylphenyl) methyl trans-2-formyl-2,2-dimethyl-cyclopropanecarboxylate in 3 ml of methanol was added. After stirring for 12 hours, water was added to the reaction solution, this was extracted with diethyl ether, the organic layer was dried over sodium sulfate, and then concentrated under reduced pressure conditions. The residue,
Subjected to silica gel column chromatography using hexane / ethyl acetate = 10/1 solvent as a developing solvent,
(1R) -trans-3-((E) -methoxyiminomethyl) -2,2-dimethylcyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methylphenyl) methyl (the present compound 11 ) 0.28 g (yield 46
%), And then the developing solvent is hexane / ethyl acetate =
4/1 solvent, (1R) -trans-3-((Z)
-Methoxyiminomethyl) -2,2-dimethylcyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-
4-methylphenyl) methyl (inventive compound 36)
23 g (yield 38%) was obtained.

Production Example 2 (1R) -trans-3-((E) -methoxyimino)
-2,2-dimethylcyclopropanecarboxylic acid and (1
R) -trans-3-((Z) -methoxyimino)-
1: 1 with 2,2-dimethylcyclopropanecarboxylic acid
0.63 g of a mixture of (2,3,5,6-tetrafluorophenyl) methanol (0.78 g), triphenylphosphine (1.16 g), and tetrahydrofuran (15 ml) with stirring, and 40% toluene of diisopropylazodicarboxylate. 2.4 g of solution was added. After 1 day, the reaction solution was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 3).
/) And the obtained fraction was again subjected to silica gel column chromatography (hexane / ethyl acetate = 10 /
(1R) -trans-3-((E) -methoxyiminomethyl) -2,2-dimethylcyclopropanecarboxylic acid (2,3,5,6-tetrafluorophenyl) methyl (the present invention). Compound 9) 0.53 g (yield 42
%), Then (1R) -trans-3-((Z))
-Methoxyiminomethyl) -2,2-dimethylcyclopropanecarboxylic acid (2,3,5,6-tetrafluorophenyl) methyl (inventive compound 34) 0.47 g (yield 37%) was obtained.

Production Example 3 (1R) -cis-3-((E) -methoxyimino)-
2,2-Dimethylcyclopropanecarboxylic acid and (1R)
0.81 g of a 1: 1 mixture with cis-3-((Z) -methoxyimino) -2,2-dimethylcyclopropanecarboxylic acid, 1- (chloromethyl) -2,3,5,6-
A mixed liquid of 1.01 g of tetrafluoro-4-methylbenzene, 1.1 g of triethylamine and 15 ml of N, N-dimethylformamide was stirred at 80 ° C for 3 hours. After cooling to room temperature, water was added to the reaction solution, and this was extracted with tert-butyl methyl ether. The organic layer was dried over sodium sulfate, concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10/1) to give (1R) -cis-3-.
((E) -Methoxyiminomethyl) -2,2-dimethylcyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methylphenyl) methyl (the present compound 6
1) and (1R) -cis-3-((Z) -methoxyiminomethyl) -2,2-dimethylcyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methylphenyl) methyl (the present A 1: 1 mixture with the invention compound 86) was obtained (yield 82%). Production Example 4 (1R) -trans-3-formyl-2,2-dimethyl-cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methylphenyl) methyl 1.97 g, tetrahydrofuran 25 ml, water 5 ml , Methanol 5m
0.68 g of hydroxylamine hydrochloride was added to a mixed solution of 1 and 2 g of pyridine, and the mixture was stirred. After 1 day, the reaction solution was concentrated under reduced pressure, water was added to the residue, and this was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and then concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 4/1) to give (1R) -trans-3-((E) -hydroxyiminomethyl) -2,2-dimethylcyclopropanecarboxylic acid. 1.09 g (yield 53%) of (2,3,5,6-tetrafluoro-4-methylphenyl) methyl (inventive compound 3) was obtained, and then (1R) -trans-3-
((Z) -hydroxyiminomethyl) -2,2-dimethylcyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methylphenyl) methyl (inventive compound 28) 0.83 g (yield 40 %) Was obtained. Production Example 5 (1R) -trans-3-((E) -hydroxyiminomethyl) -2,2-dimethylcyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methylphenyl) methyl 0. 37 g, dimethylformamide 5 ml,
To a mixed solution of 1.0 g of propyl iodide, 0.05 g of a 60% sodium hydride paraffin oil suspension was added with stirring. One day later, 0.1 M hydrochloric acid was added to the reaction solution, this was extracted with toluene, and the organic layer was dried over sodium sulfate and then concentrated under reduced pressure. The residue is subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate =
10/1), (1R) -trans-3-((E))
-Propoxyiminomethyl) -2,2-dimethylcyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methylphenyl) methyl (inventive compound 20)
0.26 g (yield 62%) was obtained.

Examples of the compounds of the present invention represented by the general formula 2 are shown in Tables 1 to 16 together with the compound numbers, but the compounds of the present invention are not limited to these examples.

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

[Table 4]

[0029]

[Table 5]

[0030]

[Table 6]

[0031]

[Table 7]

[0032]

[Table 8]

[0033]

[Table 9]

[0034]

[Table 10]

[0035]

[Table 11]

[0036]

[Table 12]

[0037]

[Table 13]

[0038]

[Table 14]

[0039]

[Table 15]

[0040]

[Table 16] [In Tables 1 to 16, in the column labeled "steric configuration of acid component", the absolute configuration at the 1-position of the cyclopropane ring of the general formula 2, the substituent at the 1-position of the cyclopropane ring and 3
It describes the relative configuration at the substituents at position and the relative configuration at the double bond of the substituents at position 3 on the cyclopropane ring. ]

The physical properties of the compound of the present invention are shown below. The present compound 3 ¹ H-NMR (CDCl ₃ , TMS) δ
1.21 (3H, s, 1.30 (3H, s), 1.87
(1H, d, J = 5.5), 2.21 (1H, dd, J
= 7.1, 5.5), 2.29 (3H, t, J = 2.
1), 5.22 (2H, s), 6.99 (1H, s),
7.26 (1 H, d, J = 7.1) Compound of the present invention 9 ¹ H-NMR (CDCl ₃ , TMS) δ
1.21 (3H, s), 1.29 (3H, s), 1.8
8 (1H, d, J = 5.4), 2.21 (1H, dd,
J = 7.2, 5.4), 3.83 (3H, s), 5.2
4 (2H, brs), 7.10 (1H, tt, J = 9.
7, 7.4), 7.19 (1H, d, J = 7.2) The present compound 10 ¹ H-NMR (CDCl ₃ , TMS)
δ1.21 (3H, s), 1.29 (3H, s), 1.
87 (1H, d, J = 5.4), 2.21 (1H, d
d, J = 7.5, 5.4), 3.83 (3H, s),
5.21 (2H, s), 7.19 (1H, d, J = 7.
5) The present compound 11 ¹ H-NMR (CDCl ₃ , TMS)
δ 1.20 (3H, s), 1.29 (3H, s), 1.
87 (1H, d, J = 5.5), 2.21 (1H, dd,
J = 7.5, 5.5), 2.29 (3H, t, J = 2.
1), 3.83 (3H, s), 5.21 (2H, br)
s), 7.18 (1 H, d, J = 7.5) Compound of the present invention 15 ¹ H-NMR (CDCl ₃ , TMS)
δ 1.20 (3H, s), 1.29 (3H, s), 1.
86 (1H, d, J = 5.5), 2.21 (1H, d
d, J = 7.4, 5.5), 3.83 (3H, s),
4.10 (3H, t, J = 1.5), 5.18 (1H,
t, J = 1.4), 5.19 (1H, t, J = 1.
4), 7.19 (1 H, d, J = 7.4) Compound of the present invention 20 ¹ H-NMR (CDCl ₃ , TMS)
δ 0.92 (3H, t, J = 7.6), 1.20 (3
H, s), 1.29 (3H, s), 1.65 (2H, q
t, J = 7.6, 6.8), 1.86 (1H, d, J =
5.5), 2.21 (1H, dd, J = 7.4, 5.
5), 2.29 (3H, t, J = 2.0), 3.97.
(2H, t, J = 6.9), 5.21 (2H, br
s), 7.20 (1 H, d, J = 7.4) Compound of the present invention 24 ¹ H-NMR (CDCl ₃ , TMS)
δ 1.20 (3H, s), 1.29 (3H, s), 1.
87 (1H, d, J = 5.4), 2.20 (1H, d
d, J = 7.3, 5.4), 2.29 (3H, t, J =
2.1), 4.53 (2H, dt, J = 5.8, 1.
4), 5.21 (2H, br s), 5.22 (1H,
dd, J = 10.4, 1.6), 5.29 (1H, d
d, J = 17.1, 1.6), 5.97 (1H, dd
t, J = 17.1, 10.4, 5.8), 7.24 (1
H, d, J = 7.3) Compound of the present invention 28 ¹ H-NMR (CDCl ₃ , TMS)
δ 1.24 (3H, s), 1.32 (3H, s), 1.
77 (1H, d, J = 5.7), 2.29 (3H, t,
J = 2.2), 2.76 (1H, dd, J = 7.7,
5.7), 5.23 (2H, s), 6.41 (1H,
d, J = 7.7), 7.33 (1H, s) Compound of the present invention 34 ¹ H-NMR (CDCl ₃ , TMS)
δ1.23 (3H, s), 1.30 (3H, s), 1.
76 (1H, d, J = 5.5), 2.70 (1H, d
d, J = 7.8, 5.5), 3.89 (3H, s),
5.25 (2H, br s), 6.31 (1H, d, J
= 7.8), 7.10 (1H, tt, J = 9.7, 7.
4) Compound of the present invention 35 ¹ H-NMR (CDCl ₃ , TMS)
δ1.23 (3H, s), 1.29 (3H, s), 1.
74 (1H, d, J = 5.5), 2.69 (1H, d
d, J = 7.9, 5.5), 3.89 (3H, s),
5.22 (2H, br s), 6.31 (1H, d, J
= 7.9) Compound of the present invention 36 ¹ H-NMR (CDCl ₃ , TMS)
δ1.23 (3H, s), 1.30 (3H, s), 1.
76 (1H, d, J = 5.6), 2.29 (2H, t,
J = 2.1), 2.69 (1H, dd, J = 7.8,
5.6), 3.89 (3H, s), 5.23 (2H, b)
rs), 6.31 (1H, d, J = 7.8) The present compound 40 ¹ H-NMR (CDCl ₃ , TMS)
δ1.23 (3H, s), 1.30 (3H, s), 1.
75 (1H, d, J = 5.5) 2.70 (1H, dd,
J = 7.9, 5.5), 3.89 (3H, s), 4.1
0 (3H, t, J = 1.5), 5.19 (1H, t, J
= 1.5), 5.20 (1H, t, J = 1.5), 6.
31 (1H, d, J = 7.9) Compound of the present invention 49 ¹ H-NMR (CDCl ₃ , TMS)
δ1.22 (3H, s), 1.30 (3H, s), 1.
75 (1H, d, J = 5.5), 2.29 (3H, t,
J = 2.1), 2.73 (1H, dd, J = 7.8,
5.5), 4.59 (2H, br d, J = 5.7),
5.21 (1H, dd, J = 10.4, 1.5), 5.
23 (2H, br s), 5.29 (1H, dd, J =
17.3, 1.5), 5.99 (1H, ddt, J = 1
7.3, 10.4, 5.7), 6.35 (1H, d, J
= 7.8) 1: 1 mixture of the compound 14 of the present invention and the compound 39 of the present invention
¹ H-NMR (CDCl ₃ , TMS) δ1.21 (1.
5H), 1.23 (1.5H), 1.29 (1.5H,
s), 1.30 (1.5H, s), 1.75 (0.5)
H, d, J = 5.4), 1.87 (0.5H, s),
2.21 (0.5H, dd, J = 7.2, 5.6),
2.69 (0.5H, dd, J = 7.6, 5.4),
3.41 (3H, s), 3.82 (1.5H, s),
3.89 (1.5H, s), 4.59 (2H, s),
5.24 (2H, s), 6.31 (0.5H, d, J =
7.8), 7.19 (0.5H, d, J = 7.2) 1: 1 mixture of the compound 23 of the present invention and the compound 48 of the present invention
¹ H-NMR (CDCl ₃ , TMS) δ 1.20 (1.
5H, s), 1.22 (1.5H, s), 1.30 (3
H, s), 1.78 (0.5H, d, J = 5.6),
1.92 (0.5H, d, J = 5.4), 2.19
(0.5H, dd, J = 7.1, 5.4), 2.29
(3H, t, J = 2.1), 2.66 (0.5H, d
d, J = 7.5, 5.6), 4.32 to 4.48 (2
H, m), 5.23 (2H, br s), 6.42
(0.5H, d, J = 7.5), 7.34 (0.5H,
d, J = 7.1) 1: 1 mixture of the compound 59 of the present invention and the compound 84 of the present invention
¹ H-NMR (CDCl ₃ , TMS) δ 1.24 (1.
5H, s), 1.25 (1.5H, s), 1.32 (3
H, s), 1.86 (0.5H, d, J = 8.5),
1.89 (0.5H, d, J = 8.7), 2.01
(0.5H, dd, J = 9.0, 8.5), 2.48
(0.5H, dd, J = 8.7, 7.7), 3.84
(1.5H, s), 3.89 (1.5H, s), 5.2
3 (2H, br s), 6.99 (0.5H, d, J =
7.7), 7.10 (1H, tt, J = 9.6, 7.
4), 7.68 (0.5H, d, J = 9.0) 1: 1 mixture of the compound 61 of the present invention and the compound 86 of the present invention
¹ H-NMR (CDCl ₃ , TMS) δ1.23 (1.
5H, s), 1.24 (1.5H, s), 1.32 (3
H, s), 1.85 (0.5H, d, J = 8.7),
1.88 (0.5H, d, J = 8.7), 2.00
(0.5H, t, J = 8.7), 2.29 (3H, t,
J = 2.1), 2.47 (0.5H, dd, J = 8.
7, 7.9), 3.84 (1.5H, s), 3.89.
(1.5H, s), 5.20 (2H, brs), 6.9
9 (0.5H, d, J = 7.9), 7.69 (0.5
H, d, J = 8.7) 1: 1 mixture of the present invention compound 65 and the present invention compound 90
¹ H-NMR (CDCl ₃ , TMS) δ1.23 (1.
5H, s), 1.25 (1.5H, s), 1.32 (3
H, s), 1.84 (0.5H, d, J = 8.6),
1.88 (0.5H, d, J = 8.6), 2.00
(0.5H, dd, J = 8.9, 8.6), 2.48
(0.5, dd, J = 8.6, 7.9), 3.84
(1.5H, s), 3.89 (1.5H, s), 4.1
0 (3H, t, J = 1.5), 5.17 (2H, t, J
= 1.4), 7.00 (0.5H, d, J = 7.9),
7.68 (0.5H, d, J = 8.9) Inventive compound 214 Inventive compound 239 3: 2 mixture
¹ H-NMR (CDCl ₃ , TMS) δ1.211.8
H, s), 1.23 (1.2H), 1.30 (3H,
s), 1.78 (0.4H, d, J = 5.5), 1.9.
2 (0.6H, d, J = 5.5), 2.20 (0.6
H, dd, J = 7.2, 5.5), 2.67 (0.4
H, dd, J = 7.5, 5.5), 4.08 (1.2
H, t, J = 1.5), 4.10 (1.8H, t, J =
1.5), 4.32 to 4.48 (2H, m), 5.18
~ 5.22 (2H, m), 6.42 (0.4H, d, J
= 7.6), 7.34 (0.6 H, d, J = 7.2) 3: 2 mixture of the compound 219 of the present invention and the compound 244 of the present invention ¹ H-NMR (CDCl ₃ , TMS) δ 1.20
(1.8H, s), 1.23 (1.2H), 1.29
(1.8H, s), 1.31 (1.2H, s), 1.7
5 (0.4H, d, J = 5.5), 1.87 (0.6
H, d, J = 5.5, 2.23 (0.6H, dd, J)
= 7.5, 5.5), 2.73 (0.4H, dd, J =
7.8, 5.5), 4.10 (3H, t, J = 1.
5), 4.52 (1.2H, dt, J = 5.8, 1.
3), 4.59 (0.8H, dt, J = 5.6, 1 ..
4), 5.18 to 5.33 (4H, m), 5.89 to
6.07 (1H, m), 6.35 (0.4H, d, J =
7.8), 7.24 (0.6H, d, J = 7.5)

Next, formulation examples are shown. In addition, a part represents a weight part and the compound of this invention is shown by the compound number of Table 1-Table 16.

Formulation Example 1 Emulsion 10 parts of each of the compounds 1 to 400 of the present invention were mixed with 35 parts of xylene.
Parts and 35 parts of dimethylformamide, 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzene sulfonate are added thereto, and well mixed with stirring to obtain 10% emulsions of each. Formulation Example 2 Wettable powder 20 parts of each of the compounds 1 to 400 of the present invention, 4 parts of sodium lauryl sulfate, 2 parts of calcium ligninsulfonate,
20 parts of synthetic hydrous silicon oxide fine powder and 54 parts of silicon earth are added into a mixture and mixed by stirring with a juice mixer to obtain each 20% wettable powder. Formulation Example 3 Granules To 5 parts of each of the compounds 1 to 400 of the present invention, 5 parts of synthetic hydrous silicon oxide fine powder, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 55 parts of clay are added and mixed thoroughly with stirring. Then, an appropriate amount of water is added to these mixtures, and the mixture is further stirred, granulated by a granulator, and air-dried to obtain each 5% granule. Formulation Example 4 Dust 1 part of each of the compounds of the present invention 1 to 400 was dissolved in an appropriate amount of acetone, and 5 parts of synthetic hydrous silicon oxide fine powder, PAP
0.3 parts of clay and 93.7 parts of clay were added, and the mixture was stirred and mixed with a juice mixer, and acetone was removed by evaporation to obtain 1 part of each.
% Powder is obtained. Formulation Example 5 Flowable agent 20 parts of each of the compounds 1 to 400 of the present invention, 28.5 parts of an aqueous solution containing 1.5 parts of sorbitan trioleate, and 2 parts of polyvinyl alcohol are mixed and finely pulverized with a sand grinder (particle size 3 μ or less). After that, 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate is added thereto, 10 parts of propylene glycol is further added, and the mixture is stirred and mixed to obtain each 20% flowable agent. Formulation Example 6 Oil agent 0.1 parts of each of the compounds 1 to 400 of the present invention is dissolved in 10 parts of dichloromethane, and this is mixed with 89.9 parts of deodorized kerosene to obtain each 0.1% oil agent.

Formulation Example 7 Oily Aerosol 1 part of each of the compounds 1 to 400 of the present invention, dichloromethane 5
Parts and deodorizing kerosene (34 parts) are mixed and dissolved, filled into an aerosol container, a valve portion is attached to the container, and 60 parts of a propellant (liquefied petroleum gas) is pressure-filled through the valve portion to each oil-based aerosol. To get Formulation Example 8 Aqueous aerosol 0.6 parts of each of the compounds 1 to 400 of the present invention, xylene 5
Parts, deodorizing kerosene 3.4 parts and emulsifiers {Atmos 300
(Registered trade name of Atlas Chemical Co., Ltd.)} 50 parts of pure water mixed with 1 part is filled in an aerosol container, a valve part is attached to the container, and 40 parts of propellant (liquefied petroleum gas) is passed through the valve part. To obtain each aqueous aerosol. Formulation Example 9 Incense Sticks 0.5 g of each of the compounds of the present invention 1 to 400 in acetone was mixed with a base material of incense sticks (tab powder: meal powder: wood powder at a ratio of 4: 3: 3) and uniformly mixed with stirring. 120 ml of water was added to 99.5 g of the incense carrier, and the mixture was thoroughly kneaded and treated to form a dried product, and the base material was air-dried to obtain an insect / acaricidal incense stick. Formulation Example 10 Electric Mosquito Repellent Mat 0.8 g of each of the compounds 1 to 400 of the present invention and 0.4 g of piperonyl butoxide are added to acetone and dissolved to make a total of 10 ml. 0.5 ml of this solution is 2.5 cm
Each electric mosquito repellent matting agent is obtained by uniformly impregnating a 1.5 cm thick, 0.3 cm thick base material for electric mat (a fibril of a mixture of cotton linter and pulp is hardened into a plate). Formulation Example 11 Liquid electric mosquito repellent 3 parts of each of the compounds 1 to 400 of the present invention are dissolved in 97 parts of deodorizing kerosene, placed in a vinyl chloride container, and the upper part of which can be heated by a heater (inorganic powder Each liquid electric mosquito repellent is obtained by inserting (sintered), which is hardened with a binder. Formulation Example 12 Heating and smoking agent 100 mg of each of the compounds 1 to 400 of the present invention is dissolved in an appropriate amount of acetone to obtain 4.0 cm × 4.0 cm, thickness 1.2 c.
m of the porous ceramic plate is impregnated to obtain each heated smoking agent. FORMULATION EXAMPLE 13 Poison bait Compounds 1 to 400 of the present invention were each mixed with 10 mg of acetone.
It is dissolved in 5 ml, and this solution is treated into 5 g of animal solid feed powder (solid feed powder for breeding and breeding CE-2, trade name of CLEA Japan, Inc.) and uniformly mixed. Then, acetone is air-dried to obtain each 0.2% poison bait.

Formulation Example 14 Mite-proof sheet Each of the compounds 1 to 400 of the present invention is dissolved in an appropriate amount of acetone and impregnated into a nonwoven fabric so that the amount of 1 g per m ² is dropped, and acetone is air-dried to obtain each mite-proof sheet. Formulation Example 15 Microcapsules After mixing 10 parts of each of the compounds 1 to 400 of the present invention, 10 parts of phenylxylylethane and 0.5 part of Sumidule L-75 (tolylene diisocyanate manufactured by Sumitomo Bayer Urethane Co.), gum arabic 20% of 10% aqueous solution and stirred with a homomixer to obtain an emulsion having an average particle size of 20 μm. Then add ethylene glycol 2
Parts are added and further reacted in a warm bath at 60 ° C. for 24 hours to obtain a microcapsule chiller. On the other hand, a thickener solution is obtained by dispersing 0.2 part of xanthan gum and 1.0 part of Veegum R (aluminum magnesium silicate manufactured by Sanyo Kasei) in 56.3 parts of ion-exchanged water. 42.5 parts of the microcapsule chiller and 57.5 parts of the thickener solution are mixed to obtain a 10% microcapsule. Formulation Example 16 Normal Temperature Evaporating Agent 100 μg of each of the compounds 1 to 400 of the present invention is dissolved in an appropriate amount of acetone, and uniformly applied on a filter paper of 2 cm × 2 cm and 0.3 mm in thickness, and air-dried with acetone. To get

Next, it is shown in Test Examples that the compound of the present invention is useful as an active ingredient of a pest controlling agent. The compounds of the present invention are shown by the compound numbers in Tables 1 to 16.

Test Example 1 Insecticidal test against Spodoptera litura Compounds 9, 10 and 1 of the present invention obtained according to Formulation Example 5
1, 15, 20, 24, 34, 35, 36, 40, 4
9, 14 and 39 1: 1 mixture, 23 and 48 1:
1 mixture, 59 and 84 1: 1 mixture, 61 and 86 1: 1 mixture, 65 and 90 1: 1 mixture, 214
And 239 each of 3: 2 mixture and 219 and 244 3: 2 mixture of each flowable agent were diluted with water so that the concentration of the active ingredient was 500 ppm, and 2 ml of the diluted solution was added.
Was prepared in a polyethylene cup having a diameter of 11 cm.
3 g of artificial feed (Insector LF: manufactured by Nippon Nosan Kogyo Co., Ltd.) was soaked. Among them is Spodoptera litura (Spod
(Optera litura) Five fourth-instar larvae were released, and the life and death of the larvae were examined 6 days later, and the mortality rate was determined. All the tested compounds of the present invention showed a mortality rate of 100%.

Test Example 2 Insecticidal test against cotton aphid Cucumber planted in polyethylene cup (first true leaf development stage)
The true leaves were inoculated with leaf pieces of which the cotton aphid was parasitic. One day after release, the compounds 9, 10, 11, 20, 35, 36, 49, 14 and 39 of the present invention obtained according to Formulation Example 5
1: 1 mixture with, 1: 1 mixture with 23 and 48, 59
1: 1 mixture of 61 and 86, 1: 1 mixture of 61 and 86, 1: 1 mixture of 65 and 90, 3: 2 mixture of 214 and 239 and 3: 2 mixture of 219 and 244, respectively. Of the flowable agent is diluted with water so that the active ingredient concentration is 500 ppm, and the diluted solution is 20 m per cup.
l sprayed. 6 days after spraying the drug solution, check the number of insects,
The control value was calculated by the formula 1.

[Formula 1] Control value = {1- (Cb × Tai) / (Tb × C
ai)} × 100 where Cb: the number of insects before treatment in the untreated section Cai: the number of insects in the untreated section observed Tb: the number of insects in the experimental section before treatment Tai: the number of insects observed in the experimental section As a result, all of the tested compounds of the present invention showed a control value of 90 or more.

Test Example 3 Insecticidal test against housefly The same size filter paper was laid on the bottom of a polyethylene cup having a diameter of 5.5 cm, and the compound of the present invention 9, 1 obtained according to Formulation Example 5
0, 11, 15, 20, 24, 34, 35, 36, 4
0, 49, 14 and 39 1: 1 mixture, 23 and 48 1: 1 mixture, 59 and 84 1: 1 mixture, 61 and 86 1: 1 mixture, 65 and 90 1 : 1 mixture,
3: 2 mixture of 214 and 239 and 219 and 244
Each of the flowable agents of 3: 2 mixture with and was diluted with water so that the active ingredient concentration was 500 ppm, 0.7 ml of the diluted solution was dropped on a filter paper, and 30 mg of sucrose was used as a bait.
Was put evenly. Housefly (Mu
10 female adults were released and the lid was closed. 24
After a lapse of time, their life and death were investigated and the mortality rate was calculated. As a result, all of the tested compounds of the present invention showed 100% mortality.
showed that.

Test Example 4 Insecticidal test against German cockroaches A polyethylene cup having a diameter of 5.5 cm was covered with a filter paper of the same size, and the compound of the present invention 9 or 1 obtained according to Formulation Example 5 was used.
0, 11, 15, 20, 24, 34, 35, 36, 4
0, 49, 14 and 39 1: 1 mixture, 23 and 48 1: 1 mixture, 59 and 84 1: 1 mixture, 61 and 86 1: 1 mixture, 65 and 90 1 : 1 mixture,
3: 2 mixture of 214 and 239 and 219 and 244
Each of the flowable agents of 3: 2 mixture with and was diluted with water so that the active ingredient concentration was 500 ppm, 0.7 ml of the diluted solution was dropped on a filter paper, and 30 mg of sucrose was used as a bait.
Was put evenly. Two adult German cockroaches (Blattella germanica) were released in a polyethylene cup and the lid was closed. After 6 days, the life and death were investigated and the mortality rate was calculated. As a result, all of the compounds of the present invention tested had a mortality rate of 100.
%showed that.

Test Example 5 Insecticidal test against Culex pipiens Compounds 3, 9, 10 of the present invention obtained according to Formulation Example 5
11, 15, 20, 24, 28, 34, 35, 36, 4
0, 49, 14 and 39 1: 1 mixture, 23 and 48 1: 1 mixture, 59 and 84 1: 1 mixture, 61 and 86 1: 1 mixture, 65 and 90 1 : 1 mixture,
3: 2 mixture of 214 and 239 and 219 and 244
Each of the flowable agents of the 3: 2 mixture of and was diluted with water so that the active ingredient concentration was 500 ppm, and 0.7 ml of the diluted solution was added to 100 ml of ion-exchanged water (active ingredient concentration 3.5 ppm). The last larva of Culex pipiens 2 in the liquid
0 animals were released, and one day later, their life and death were investigated and the mortality rate was calculated. As a result, all of the tested compounds of the present invention showed a mortality rate of 100%. Compound number:

Test Example 6 Insecticidal test by volatilization at room temperature against carp sorghum Polyethylene cup (bottom diameter 10 cm, opening diameter 12.5 cm, height 9.5 cm, volume 950 cm ³ )
2 × 2 cm of wool muslin cloth and 10 medium-instar larvae of Koga were placed in the bottom of the mixture, and the compound of the present invention 9, 10, 11, 34, 35, 36, 23 and 48 obtained according to Formulation Example 1 1 mixture, 1: 1 mixture of 59 and 84 and 6
Each cold vaporizer of each 1: 1 mixture of 1 and 86 was hung from the lid and sealed. After being left for 1 week at a temperature of 25 ° C., the survival, agony, and dead insect numbers of the Koga middle-aged larvae were examined to determine the rate of bitter mortality, and the feeding damage of the woolmusulin cloth was also examined.
Further, as a control compound, (1R) -cis-3- (cyclobutoxyiminomethyl) -2,2-dimethylcyclopropanecarboxylic acid (2,3,4,5,6) described in JP-A-56-7750. -Pentachlorophenyl) methyl (hereinafter referred to as control compound A) and (1R) -trans-3- (cyclopentoxyiminomethyl) -2,2-
Dimethylcyclopropanecarboxylic acid (2, 3, 4, 5,
Using 6-pentafluorophenyl) methyl (hereinafter referred to as control compound B), the same test was performed. Judgment standard of eating damage degree And The results are shown in Table 17.

[0053]

[Table 17]

Test Example 7 Mosquito coiling incense test for Culex pipiens 20 adult Culex pipiens females (70 c / s)
m cubic glass chamber (volume 0.34
m ³ ). Compounds of the present invention 9, 10, 11, 15, 20, 24, 34 obtained according to the method of Formulation Example 9,
35, 36, 40, 49, 1: 1 mixture of 14 and 39, 1: 1 mixture of 23 and 48, 1: 59 and 84.
1 g of 1 mixture of 61 and 86, 1: 1 mixture of 65 and 90 and 3: 2 mixture of 214 and 239 each of which was cut into 0.3 g and ignited from one end, Each of them was set up in the incense holder in the center of the above-mentioned chamber floor, taken out of the chamber after burning for 30 seconds.
Twelve minutes after the incense was installed, the state of knockdown of Culex pipiens was investigated. Further, the same test was carried out using the control compounds A and B as control compounds. The results are shown in Table 18.

[0055]

[Table 18]

Test Example 8 Oil Spraying Test for Housefly 20 Musca domestica adult Musca domestica (male / female = 1)
0/10) was released into a cubic glass chamber (volume 0.34 m ³ ) having a side of 70 cm. Compounds of the present invention 9, 10, 11, 15 prepared according to the method of Formulation Example 6
20, 24, 34, 35, 36, 40, 49, 14 and 3
1: 1 mixture with 9, 1: 1 mixture with 23 and 48, 5
1: 1 mixture of 9 and 84, 1: 1 mixture of 61 and 86, 1: 1 mixture of 65 and 90, 3: 2 mixture of 214 and 239 and 3: 2 mixture of 219 and 244. 0.7kg of each oil of 0.9kg with a spray gun
Sprayed at a pressure of / cm ² . Five minutes after spraying, the knockdown situation of the housefly was investigated. Further, the same test was carried out using the control compounds A and B as control compounds. The results are shown in Table 19.

[0057]

[Table 19]

[0058]

By using the compound of the present invention, an excellent pest control effect can be obtained.

Claims (9)

[Claims] 1. A general formula: ## STR1 ## [In the formula, R represents a hydrogen atom, a C1 to C3 alkyl group optionally substituted with a halogen atom, an allyl group optionally substituted with a halogen atom or a propargyl group optionally substituted with a halogen atom, X is a hydrogen atom, a halogen atom, or C1 to be optionally substituted with a halogen atom.
C3 alkyl group, C2 to C3 alkenyl group optionally substituted with halogen atom, C2 to C3 alkynyl group optionally substituted with halogen atom, C1 to C3 alkoxy group optionally substituted with halogen atom, halogen An optionally substituted C1-C3 alkylthio group,
Or, (C1 optionally substituted with a halogen atom
C3 alkoxy) represents a methyl group. ] The ester compound shown by these. 2. The ester compound according to claim 1, wherein the 1-position of the cyclopropane ring of the general formula 1 is in the R configuration. 3. The ester compound according to claim 1, wherein in the cyclopropane ring of the general formula 1, the configuration of the substituent at the 1-position and the configuration of the substituent at the 3-position is trans configuration. 4. The ester compound according to claim 1, wherein in the cyclopropane ring of the general formula 1, the steric configuration of the substituent at the 1-position and the substituent at the 3-position is cis. 5. The ester compound according to claim 1, wherein in the general formula 1, R is a methyl group. 6. The ester compound according to claim 1, wherein in the general formula 1, X is a hydrogen atom. 7. The ester compound according to claim 1, wherein in the general formula 1, X is a methyl group. 8. The ester compound according to claim 1, wherein in the general formula 1, X is a methoxy group. 9. A pest control agent comprising the ester compound according to any one of claims 1 to 8 as an active ingredient.