JP2001302590A - Ester compound and insecticide with the same as active ingredient - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent insecticide, and to provide a compound usable as an active ingredient for the insecticide. SOLUTION: This compound is shown by the formula. The other objective insecticide is characterized by containing this compound as active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

BACKGROUND OF THE INVENTION 2,2,3-Trimethylcyclopropanecarboxylic acid 2,3,5,6-tetrafluorofluoroethylene is used as an active ingredient of an insect repellent having excellent durability in clothing. -4-Methylbenzyl ester is known (JP-A-7-17916). In general, a high insecticidal effect is often required as an active ingredient of an agent for controlling insect pests, including clothing, and it is desired to develop a compound which exhibits an insecticidal effect in a smaller amount and has a so-called excellent insecticidal effect. It is rare. on the other hand,
2,2,3-trimethylcyclopropanecarboxylic acid
Although the insect repellent for clothing containing 2,3,5,6-tetrafluoro-4-methylbenzyl ester as an active ingredient is excellent in terms of the persistence of the effect as described above, the present inventors conducted a test to show the insecticidal effect. Did not always have sufficient performance. An object of the present invention is to provide an excellent insecticide and to provide a compound which can be an active ingredient of the insecticide.

[0003]

Under such circumstances, the present inventors have conducted intensive studies and as a result, have found that the compound represented by the following formula 2 has excellent insecticidal activity, and have reached the present invention. That is, the present invention provides

Embedded image (Hereinafter referred to as the present compound) and an insecticide containing the compound as an active ingredient (hereinafter referred to as the present insecticide).

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention can be produced, for example, by the following (Production method 1), (Production method 2) and the like. (Manufacturing method 1) Formula 3

Embedded image And an alcohol compound represented by the formula

Embedded image The reaction is usually carried out in the presence of a condensing agent or in the presence of an acid catalyst in a solvent, usually in the presence of a 2,2,3-trimethylcyclopropanecarboxylic acid. Examples of the condensing agent used in the reaction include dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and the like. As the acid catalyst used in the reaction,
For example, inorganic acids such as sulfuric acid, and sulfonic acids such as p-toluenesulfonic acid and methanesulfonic acid are exemplified. In this reaction, a solvent inert to the reaction can be used. Specific examples include hydrocarbons such as toluene and hexane, ethers such as diethyl ether and tetrahydrofuran, and halogens such as dichloromethane and 1,2-dichloroethane. Hydrocarbons, and mixed solvents thereof. The range of the reaction time is usually from instant to 72 hours. The reaction temperature range is from -20 ° C to 100 ° C (when the boiling point of the solvent is 100 ° C or lower, the boiling point of the solvent used in the reaction). The alcohol compound represented by the formula (3) used in the reaction can achieve its purpose with 1 mol per 1 mol of the carboxylic acid represented by the formula (4).
It can vary in the range of 5 moles. When this reaction is performed in the presence of a condensing agent, the amount of the condensing agent used in the reaction is
Usually, 1 mole per 1 mole of the carboxylic acid of the formula
Although it is molar, it can vary depending on the circumstances of the reaction. When this reaction is carried out in the presence of an acid catalyst, the acid catalyst used in the reaction may be used in any amount according to the situation of the reaction. After the reaction, the compound of the present invention can be obtained by performing ordinary post-treatment operations such as concentration of the reaction mixture after extraction with an organic solvent and, if necessary, further purification operations such as chromatography and distillation. it can.

(Production method 2) An alcohol compound represented by the formula (3) and a reactive derivative of 2,2,3-trimethylcyclopropanecarboxylic acid represented by the formula (4) (acid halide, acid anhydride, etc.) Reaction Method The reaction is usually performed in a solvent in the presence of a base.
Examples of the base used in the reaction include organic bases such as triethylamine, pyridine, N, N-diethylaniline, 4-dimethylaminopyridine, and diisopropylethylamine. In this reaction, a solvent inert to the reaction may be used, and specific examples thereof include hydrocarbons such as toluene and hexane, ethers such as diethyl ether and tetrahydrofuran, and halogens such as dichloromethane and 1,2-dichloroethane. Hydrocarbons and mixed solvents thereof can be used. The range of the reaction time is usually from instant to 72 hours. The reaction temperature range is usually −20 ° C.
To 100 ° C (when the boiling point of the solvent is 100 ° C or lower, the boiling point of the solvent used in the reaction). The alcohol compound represented by the formula (3) used in the reaction can achieve its purpose with 1 mol per 1 mol of the carboxylic acid represented by the formula (4). Can change. The base used in the reaction can achieve the purpose of 1 mol per 1 mol of the reactive derivative of the carboxylic acid represented by the formula 4, but can be changed according to the reaction situation. After the reaction, the compound of the present invention is subjected to ordinary post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and then concentrating the mixture, and, if necessary, further performing purification operations such as chromatography and distillation. Obtainable.

The compounds of the present invention include isomers relating to two asymmetric carbon atoms present on the cyclopropane ring, ie, (1R) -trans, (1S) -trans,
(1R) -cis form and (1S) -cis form {wherein
(1R) and (1S) mean the position and absolute configuration on the cyclopropane ring, and trans and cis mean the relative configuration of the 1 and 3 positions on the cyclopropane ring. Although｝ is present, the compound of the present invention includes a single compound of each isomer and a mixture of any ratio of each isomer. The alcohol compound represented by Formula 3 is a known compound (for example, JP-A-57-123146). Further, the carboxylic acid represented by the formula 4 is, for example, Agr.
Biol. Chem. , 37 (10), 2241-22
44 (1973), Agr. Biol. Chem. , 3
1 (10), 1143-1150 (1967). The reactive derivative of the carboxylic acid represented by the formula (4) can be produced from the carboxylic acid represented by the formula (4) in a usual manner. Can be manufactured.

The pests targeted by the compounds of the present invention include:
For example, the following pests can be mentioned. Lepidopteran pests, Japanese moths (Pycium persica, P. persicae, etc.), armyworms (Spodoptera litura, Acacia catechus, etc.), white butterflies (Pycaenidae, etc.), antelopes (Pat. , Agrotis pest
is spp.) (Kabayaaga, Tamanayaga, etc.), Helicoverpa spp., Heliotis pest
(Heliothis spp.), Convolvulus, Ichimondiseceli, Iga, Koiga, etc. Diptera pests House mosquitoes (Acalyx, Aedes albopictus, etc.), Aedes (Aedes aegypti, Aedes albopictus, etc.), Anopheles (Aesculus, etc.), Musca domestica , House flies, slime flies, etc.), blowflies, flies, flies (flies, onions, etc.), fruit flies, drosophila, drosophila,
Tabes, blackflies, flies, flies, etc. Reptile insects German cockroaches, black cockroaches, cockroaches, brown cockroaches, cockroach cockroaches, etc. Hymenoptera pests Ants, wasps, arigatas, and wasps (eg, wasps) Lepidopteran pests, such as dog flea, cat flea, and human flea Lice pests, human lice, lice, head lice, white lice, etc. Isoptera pests, etc. (Mite mite, house mite, etc.), mites (stag mite, mites mite, etc.), dust mite, marmite mite, house mite, spider mite (red spider mite, Kanzawa spider mite, mandarin orange) Mites, Ringohadani, etc.), ticks (Haemaphysalis longicornis, etc.). Hemiptera pests Planthoppers (Pyrocarpus terrestris, brown planthoppers, brown planthoppers, etc.), leafhoppers (butterfly leafhoppers, leafhopper leafhoppers, etc.), aphids, stinkbugs, whiteflies, scale insects, weevil insects, whitefly Worms (Western corn root worm, Southern corn root worm, etc.), Scarabaeids (Duchane buoy, etc.), Weevils (Koku weevil, Rice weevil, Watami weevil, Azuki weevil, etc.), Thorn beetles (Scarabaeidae, etc.) ), Leaf beetles (rice beetle, beetle flea beetle, etc.), beetles, epiracuna (Epilachna spp.) (E.g., ladybird beetle), leaf beetle Naga Shinkuimushi class, beetles such, Hime beetle, varied carpet beetle, Aoba ants play Staphylinidae, etc. Thysanoptera pests South thrips, western flower thrips, Hana thrips, etc. Orthoptera pest mole crickets, grasshoppers, etc.

[0008] In the present application, the insecticide for household quarantine refers to the following insecticides among insecticides. House mosquitoes (Scaly mosquito, Kogata mosquito, etc.), Aedes (Aedes aegypti, Aedes albopictus, etc.), Anopheles (Sinama anopheles, etc.), midges, house flies (Musca domestica,
House flies, Dermatophagidae, etc.), blowflies, flies, flies, flies, flies, black flies, flies, brassicae, ants, hornets, wasps, wasp mites (Dermatophagoides farinae, Dermatophagoides farinae, etc.) Acarid mites, etc.), acarid mites (e.g., mites), crab mites (e.g., stag beetle, mites mites), maricidae, house mite,
Ticks (eg, Haemaphysalis longicornis), Tenebrion beetles (eg, beetles beetles), beetles, giant beetles, longhorn beetles, long-spotted beetles, sword beetles, stalks, squirrels, squirrels, swordfish Cockroaches, German cockroaches, dog flea, cat flea, human flea, human lice, lice, lice, head lice, body lice, yamato termite, house termite, bed bug, lice beetle, beetle beetle, beetle beetle, weevil, azuki weevil

Although the compound of the present invention can be used as it is, the insecticide of the present invention is usually used after being formulated.
Examples of the preparation include solid preparations such as granules, powders and wettable powders, and liquid preparations such as oils, emulsions, flowables and microcapsules. Formulation of the insecticide of the present invention,
The compound of the present invention can be obtained by blending a carrier, a surfactant, a fixing agent, a thickener, a stabilizer, and the like, followed by pulverization and processing. Examples of the carrier used in the formulation include solid carriers such as clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fusami clay, acid clay, etc.), talc, ceramics, and other inorganic minerals (cellulose). Site, quartz, activated carbon, calcium carbonate,
Hydrated silica, montmorillonite, etc.), liquid carrier, water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methyl) Naphthalene, phenylxylylethane, etc.), aliphatic hydrocarbons (hexane, cyclohexane,
Kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N -Dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethylsulfoxide, vegetable oils such as soybean oil, cottonseed oil, etc., and gaseous carriers {fluorocarbon gas, butane gas) , LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide and the like. Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers, and alkyl ethers. Polyoxyethylenated aryl ethers, polyethylene glycol Over ethers, polyhydric alcohol esters, and sugar alcohol derivatives and the like,
Examples of the fixing agent include casein, gelatin, polysaccharides (starch, gum arabic, xanthan gum, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, saccharides, and synthetic water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone). , Polyacrylic acids, etc.), examples of the thickener include polysaccharides (such as xanthan gum), and inorganic minerals (such as aluminum magnesium silicate). Examples of the stabilizer include, for example,
PAP (acidic isopropyl 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, and fatty acid ester. Examples of the method for using the insecticide of the present invention include the following methods, which can be appropriately selected depending on the dosage form of the preparation, the place of use, and the like. 1. A method of treating the preparation as it is in the habitat of the pest. 2. A method in which a preparation is diluted with a solvent such as water and then treated at a place where a pest inhabits. 3. A method in which the preparation is heated in the habitat of the pest.

Further, when the insecticide of the present invention is a household insecticide, it can be generally used as a heated fumigant, a heated smoker, a non-heated transpiration, an aerosol, a poison bait,
The compound of the present invention is preferably used as a non-heated evaporant in view of the physical properties. Here, in the present application, the heat fumigant, the heat fumigant, the non-heat fever, and the poison bait refer to preparations suitable for the use form specified as each agent name. Examples of the heat fumigant include a mosquito coil and an electric mosquito-removing mat as a solid preparation, and an absorbent core-type heat-transpiration insecticidal liquid as a liquid preparation. Examples of the heated smoker include a self-combustion smoker, a chemical reaction smoker, and a porous ceramic plate smoker as solid preparations. As a non-heated evaporant,
Examples of the solid preparation include a resin vaporizer and an impregnated paper vaporizer. Aerosols include aqueous aerosols and oily aerosols as liquid preparations. Examples of the method of formulating the compound of the present invention into a mosquito coil, an electric mosquito coil mat, a liquid absorbent core-type transpired insecticidal liquid, a heated smoker, a non-transpired agent, an aerosol, and a poison bait include the following methods. 1. When formulated into a mosquito coil or electric mosquito net, a method of impregnating the compound of the present invention into a base material such as a mosquito coil or an electric mosquito coil which does not contain an active ingredient, and molding and processing after mixing the compound of the present invention with the base material Method. 2. In the case of formulating into a liquid absorbent core-type transpired insecticidal solution: A method of diluting the compound of the present invention into a liquid carrier and formulating the compound into a liquid insecticidal solution for collecting electric mosquitoes. 3. When formulated into a heated smoker such as a self-combustion smoker, a chemically-reacted smoker, a porous ceramic plate smoker, etc. A method of formulating the compound of the present invention by mixing it with a substrate and then molding. 4. When formulated into a non-heated evaporating agent such as a resin evaporating agent or an impregnated paper evaporating agent: a method in which the compound of the present invention is mixed with a thermoplastic resin and then molded; 5. When formulated into an aerosol A method in which an aerosol container is prepared by diluting the compound of the present invention in a liquid carrier and pressurizing a propellant. 6. When formulated into poison bait A method of formulating by mixing the compound of the present invention and a base material and then molding.

[0011] As a base material of the mosquito coil, for example, wood flour,
A mixture of a vegetable powder such as cake powder and a binder such as tub powder, starch, glutein and the like can be mentioned. Examples of the base material of the electric mosquito collecting mat include those obtained by hardening a cotton linter into a plate, and those obtained by hardening a fibril of a mixture of cotton linter and pulp into a plate. 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 metal salts; Thermal decomposition stimulants such as chromate and chromate, oxygen supply agents such as potassium nitrate, flame retardants such as melamine and wheat starch, fillers such as diatomaceous earth,
And binders such as synthetic pastes. As a base material of the chemical reaction type smoke agent, for example, sulfide of an alkali metal,
Heat generating agents such as polysulfides, hydrosulfides, hydrated salts, calcium oxide, etc., catalysts such as carbonaceous materials, iron carbide, activated clay, azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenetetramine, polystyrene, polyurethane, etc. Organic foaming agents and fillers such as natural fiber pieces and synthetic fiber pieces. Examples of the base material of the non-heated evaporant include thermoplastic resins (polyester, polyamide, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, etc.), paper (filter paper). , High-quality paper, note paper, dust paper, cardboard, etc.) and cloth (nonwoven fabric, etc.). Aerosol propellants include, for example, liquefied petroleum gas, Freon gas, butane gas, and dimethyl ether. As the bait bait, for example, cereal flour, vegetable oil, sugar, bait ingredients such as crystalline cellulose, dibutylhydroxytoluene,
Examples include antioxidants such as nordihydroguaseletic acid, preservatives such as dehydroacetic acid, ingestion inhibitors such as pepper powder, and attractants such as cheese flavor, onion flavor, and peanut oil.

The insecticide of the present invention can be mixed with or used in combination with other insecticides, acaricides, repellents, synergists and the like. As such insecticides and acaricides, for example, fenitrothion [O, O-dimethyl O- (3-methyl-4
-Nitrophenyl) phosphorothioate], phenthion [O, O-dimethyl O- (3-methyl-4- (methylthio) phenyl) phosphorothioate], diazinone [O, O-diethyl-O-2-isopropyl-6] -Methylpyrimidin-4-yl phosphorothioate], chloropyrifos [O, O-diethyl-O-3,5,6-trichloro-2-pyridyl phosphorothioate], acephate [O, S- Dimethylacetylphosphoramide thioe-
G), methidathion [S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-
Ilmethyl O, O-dimethyl phosphorodithioe-
G), disulfoton [O, O-diethyl S-2-ethylthioethyl phosphorodithioate], DDVP [2,
2-dichlorovinyldimethyl phosphate], sulfophos [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-dimethoxyphospho Finothioylthio (phenyl) acetate], malathion [diethyl (dimethoxyphosphinothioylthio) succinate], trichlorfon [dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate], azinphosmethyl [S-3,4- Dihydro-4-oxo-1,
2,3-benzotriazin-3-ylmethyl O, O-
Dimethyl phosphorodithioate], monocrotophos [dimethyl (E) -1-methyl-2- (methylcarbamoyl) vinyl phosphate], ethion [O, O, O ',
Organic phosphorus compounds such as O'-tetraethyl S, S'-methylenebis (phosphorodithioate)], BPMC (2
-Sec-butylphenylmethylcarbamate], benfracarb [ethyl N- [2,3-dihydro-2,2-
Dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N-isopropyl-β-alaninate], propoxur [2-isopropoxyphenyl
N-methyl carbamate], carbosulfan [2, 3
-Dihydro-2,2-dimethyl-7-benzo [b] furanyl N-dibutylaminothio-N-methylcarbamate], carbaryl [1-naphthyl-N-methylcarbamate], mesomil [S-methyl-N-[( Methylcarbamoyl) oxy] thioacetimidate], ethiophencarb [2- (ethylthiomethyl) phenylmethylcarbamate], aldicarb [2-methyl-2- (methylthio) propionaldehyde O-methylcarbamoyloxime], oxamil [N, N -Dimethyl-2-methylcarbamoyloxyimino-2- (methylthio) acetamide], phenothiocarb [S-4-phenoxybutyl) -N, carbamate compounds such as 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-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], praletrin [(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,

N-cyano-N'-methyl-N '-(6-
N- such as chloro-3-pyridylmethyl) acetamidine
Cyanoamidine derivative, endosulfan [6, 7,
8, 9, 10, 10-hexachloro-1, 5, 5a,
6, 9, 9a-hexahydro-6,9-methano-2,
4,3-benzodioxathiepine oxide], γ-B
HC (1,2,3,4,5,6-hexachlorocyclohexane), 1,1-bis (chlorophenyl) -2,2,
Chlorinated hydrocarbon compounds such as 2-trichloroethanol,
Chlorfluazuron [1- (3,5-dichloro-4-
(3-chloro-5-trifluoromethylpyridine-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-chloro-4-trifluoromethylphenoxy) -2-fluorophenyl] -3-
(2,6-difluorobenzoyl) urea], diabenthiurone [N
Thiourea derivatives such as-(2,6-diisopropyl-4-phenoxyphenyl) -N'-tert-butylcarbodiimide], phenylpyrazole compounds, and methoxadiazone [5-methoxy-3- (2-methoxyphenyl) -1 3,4-oxadiazol-2- (3H)-
On], 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-chloropyridazine-3 (2H)
-One], fenpyroximate [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], pyrimidifen [5-chloro-N- [2- ｛4
-(2-ethoxyethyl) -2,3-dimethylphenoxydiethyl] -6-ethylpyrimidin-4-amine, milbemectin, abamectin, ivamectin, azadirachtin [AZAD] and the like.
For example, 3,4-caranediol, N, N-diethyl-
m-toluamide, 1-methylpropyl 2- (2-hydroxyethyl) -1-piperidinecarboxylate, p
Plant essential oils such as -menthane-3, 8-diol, hyssop oil and the like;
(2,3,3,3-tetrachloropropyl) ether,
N- (2-ethylhexyl) bicyclo [2,2,1] hept-5-ene-2,3-dicarboximide, α-
[2- (2-butoxyethoxy) ethoxy] (piperonyl butoxide) and the like.

The compound of the present invention can also be used as an active ingredient of a pest repellent. In this case, it can be mixed with other pest repellents, and can be used depending on the preparation and usage as a usual pest repellent. When the insecticide of the present invention is used as an insecticide for home epidemics, from the viewpoint of the physical properties of the compound of the present invention,
It is preferably used as an insecticide for clothing as a normal-temperature volatile agent.

[0016]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Formulation Examples and Test Examples, but the invention is not limited thereto. First, Production Examples of the compound of the present invention will be shown. Production Example 4-Methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol 1.12 g, pyridine 0.47 g and tetrahydrofuran 10 ml in a ice-cooled solution of 2,2,3-trimethylcyclopropanecarboxylic acid Chloride ｛stereoisomer ratio (1R) -trans form:
(1R) -cis form: (1S) -trans form: (1S)-
After adding 0.81 g of a compound prepared by a conventional method from 2,2,3-trimethylcyclopropanecarboxylic acid and oxalyl chloride (cis-isomer = 28: 42: 12: 18), stirring was continued at room temperature for 8 hours. The reaction solution was poured into about 30 ml of ice water, and this was extracted twice with 50 ml of ethyl acetate. The ethyl acetate layers were combined, washed with saturated saline, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure to obtain a crude oil. The resulting crude oil was subjected to silica gel column chromatography to give 2,2,3-trimethylcyclopropanecarboxylic acid 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl ester (the compound of the present invention). 35 g (81% yield) were obtained. ¹ H-NMR (CDCl ₃ , TMS internal standard) δ value (pp
m): 1.10 (d), 1.14 (s), 1.20 (s)
(9H in total), 1.24 (m, 1H), 1.40
(m, 1H), 3.40 (s, 3H), 4.58 (brs,
2H), 5.19 (brs, 2H)

Next, preparation examples are shown. Parts represent parts by weight. Formulation Example 1 Emulsion 20 parts of the compound of the present invention are dissolved in 65 parts of xylene, and 15 parts of an emulsifier, Solpol 3005X (trade name of Toho Kagaku) are added and mixed well with stirring to obtain a 20% emulsion. Formulation Example 2 wettable powder 40 parts of the compound of the present invention was added to sorbol 3005X (described above) 5
Parts, and mixed well. Carplex # 80 (trade name of Shionogi & Co., Ltd., synthetic hydrous silicon oxide fine powder) 32
, 300 parts of diatomaceous earth, and stirred and mixed with a juice mixer to obtain a 40% wettable powder. Formulation Example 3 Granules 1.5 parts of the compound of the present invention and AGSORBLVM-MS
98.5 parts of 24/48 (baked product of montmorillonite manufactured by OILDRI, granular carrier having a particle size of 24 to 48 mesh) are added and mixed well to obtain 1.5% granules.

Formulation Example 4 Microcapsules 10 parts of the compound of the present invention, 10 parts of phenylxylylethane, and 0.5 part of Sumidur L-75 (tolylene diisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.) are mixed. % Aqueous solution 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 warm 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 Vegum R (aluminum magnesium silicate manufactured by Sanyo Chemical) are dispersed in 56.3 parts of ion-exchanged water to obtain a thickener solution. The above microcapsule slurry 42.5
And 57.5 parts of the thickener solution to give 10% microcapsules. Formulation Example 5 Flowable agent After mixing 10 parts of the compound of the present invention and 10 parts of phenylxylylethane, a 10% aqueous solution of polyethylene glycol 2
0 parts and stirred with a homomixer to obtain an average particle size of 3 μm.
to obtain an emulsion of m. On the other hand, Xanthan gum 0.2
Part, Vegum R (aluminum magnesium silicate manufactured by Sanyo Chemical Industries) 1.0 part is dispersed in ion-exchanged water 58.8 parts to obtain a thickener solution. 40 parts of the above emulsion and 60 parts of the thickener solution are mixed to obtain a 10% flowable agent. Formulation Example 6 Dust 5 parts of the compound of the present invention is carplex # 80 (described above) 3
Part, PAP 0.3 part and 300 mesh talc 91.7
The mixture is stirred and mixed with a juice mixer to obtain a 5% powder.

Formulation Example 7 Oil Preparation 0.1 part of the compound of the present invention is dissolved in 5 parts of dichloromethane.
This is mixed with 94.9 parts of deodorized kerosene to obtain a 0.1% oil. Formulation Example 8 Oily aerosol 1 part of the compound of the present invention, 5 parts of dichloromethane and 34 parts of deodorized kerosene are mixed and dissolved, filled in an aerosol container, a valve is attached, and a propellant (liquefied petroleum gas) is passed through the valve. 60 parts are pressurized to obtain an oily aerosol. Formulation Example 9 Aqueous Aerosol A mixture of 0.6 part of the compound of the present invention, 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of an emulsifier {Atmos 300 (registered trademark of Atlas Chemical Co.)} was mixed and dissolved in pure water. 50 parts are filled in an aerosol container, a valve part is attached, and 40 parts of a propellant (liquefied petroleum gas) is filled under pressure through the valve part to obtain an aqueous aerosol.

Formulation Example 10 Mosquito coil Incense 0.3 g of the compound of the present invention is dissolved in 20 ml of acetone, and 99.7 g of a carrier for mosquito coil (mixed in a ratio of 4: 3: 3 of tub powder: meal powder: wood powder). After stirring and mixing uniformly, water 120
Then, the resulting mixture is molded and dried to obtain a mosquito coil. Formulation Example 11 Electric mosquito collecting mat 0.8 g of the compound of the present invention and 0.4 g of piperonyl butoxide
And add acetone to make a total of 10 ml. 0.5 ml of this solution is 2.5 cm x 1.5 cm, 0.3 c thick
m is uniformly impregnated with an electric mat substrate (a fibril of a mixture of cotton linter and pulp solidified in a plate shape) to obtain an electric mosquito repellent. Formulation Example 12 Liquid Absorbent Core Type Formulation for Heat-Evaporative Insecticidal Apparatus 3 parts of the compound of the present invention is dissolved in 97 parts of deodorized kerosene, placed in a vinyl chloride container, and the upper part is heated with a heater. Is solidified with a binder and sintered) to obtain a liquid-absorbent wick-type transpiration insecticidal preparation.

Formulation Example 13 Perforated ceramic plate smoker 100 mg of the compound of the present invention was dissolved in an appropriate amount of acetone.
A porous ceramic plate having a size of 4.0 cm × 4.0 cm and a thickness of 1.2 cm is impregnated to obtain a smoke agent for the porous ceramic plate. Formulation Example 14 Impregnated paper evaporating agent 100 μg of the compound of the present invention was dissolved in an appropriate amount of acetone.
After uniformly applying to a filter paper having a size of cm × 2 cm and a thickness of 0.3 mm, acetone is air-dried to obtain an impregnated paper evaporating agent.

Next, Test Examples show that the compound of the present invention is useful as an active ingredient of an insecticide.

Test Example 1 Insecticidal test on carp moth Acetone solution of a test compound (prepared to a concentration of 1.5 μg / 0.3 μl) was treated at 0.3 μl / mouse on the dorsal central part of middle larva of carp. Thereafter, 10 middle-aged larvae of the knot moth and a 2 × 2 cm wool muslin cloth were placed in a polyethylene cup, and the mortality and the degree of food damage of the wool muslin cloth after 7 days were examined. As a comparative control compound in this test, the ratio of 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol to 2,2,3-trimethylcyclopropanecarboxylic acid chloride {stereoisomer (1R)-
Trans-form: (1R) -cis-form: (1S) -trans-form: (1S) -cis-form = 28: 42: 12: 18 ratio of stereoisomers (1R) -trans-form: (1R) -cis-form:
(1S) -trans form: (1S) -cis form = 28: 4
2,2,3 obtained from 2,2,3-trimethylcyclopropanecarboxylic acid and oxalyl chloride at 2:12:18 according to the method described in JP-A-7-17916. -Trimethylcyclopropanecarboxylic acid 4-methyl-2,3,5,6-tetrafluorobenzyl ester (hereinafter referred to as control compound) was used. The evaluation criteria for the degree of damage were +++: markedly damaged ++: slightly damaged +: slightly damaged ±: slightly damaged-: determined not damaged (2 repetitions). As a result, the section treated with the compound of the present invention showed a mortality of 100% and a degree of food damage. In contrast, the mortality rate was 0% in the group treated with the control compound.
And the degree of damage was +++.

Test Example 2 Insecticidal test on Culex pipiens Acetone solution of the test compound (prepared to a concentration of 3 μg / 0.3 μl) was applied to the back of the chest of adult Culex pipiens so that the active ingredient amount would be 3 μg / head. Thereafter, 10 adult Culex pipiens pallens were placed in a polyethylene cup, and fed with water and food. After 24 hours, the numbers of surviving insects, writhing insects and dead insects were investigated, and the number of writhing insects [｛(number of writhing insects + number of dead insects)
/ (Number of surviving insects + number of writhing insects + number of dead insects) 虫 × 100]. As a result, the plot treated with the compound of the present invention showed a mortality rate of 100%. In contrast, the group treated with the control compound had a mortality of 0% (2 replicates).

Test Example 3 Insecticidal test by evaporating at room temperature on carp moor muslin cloth of 2 × 2 cm on the bottom of polyethylene cup (diameter of bottom 10 cm, diameter of opening 12.5 cm, height 9.5 cm, volume 950 cm ³ ) And 10 larvae of the middle-aged larvae of Kiga, and sealed with an impregnated paper evaporating agent (produced according to Formulation Example 14) suspended from the lid. After being left at a temperature of 25 ° C. for one week, the container was opened, and the numbers of surviving insects, writhing insects and dead insects were examined, and the rate of mortal insects and the degree of damage to the ulmosulin cloth were examined.
The evaluation criteria for the degree of damage were +++: markedly damaged ++: slightly damaged +: slightly damaged ±: slightly damaged-: determined not damaged (2 repetitions). As a result, the section treated with the compound of the present invention exhibited a mortality rate of 100% and a degree of food damage. In contrast, the group treated with the control compound had a mortality rate of 0% and a degree of damage of +++.

[0026]

The compound of the present invention is excellent in controlling insect pests,
It is extremely useful as an active ingredient of a pest control agent, particularly a pest control agent for home protection.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA01 AA03 AB02 BJ20 BM30 BM71 BP30 BT22 4H011 AC02 AC04 BA02 BB15 BC01 BC02 BC03 BC05 BC08 BC18 BC19 BC20 DA02 DA06 DA07 DA10 DA15 DA16 DD05 DE05 DF04 DH05 DH14

Claims (3)

[Claims] [Claim 1] Formula 1 A compound represented by the formula: 2. An insecticide comprising the compound according to claim 1 as an active ingredient. 3. An insecticide for household epidemics, comprising the compound according to claim 1 as an active ingredient.