JPH0867653A - Ester compound, pest controlling agent containing the same as active ingredient and intermediate for producing the same - Google Patents

Abstract

PURPOSE: To obtain an ester compound useful as an active ingredient, etc., of a pest controlling agent. CONSTITUTION: This compound of formula I [R1 is methyl or H; R2 is a 1-6C haloalkyl; R3 is a residue of pyrethric acid (a part except carboxyl group)], e.g. (RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxo-2-cyclopenten-1-yl (1R)-trans-3-(2,2- dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate. The compound of formula I is obtained by reacting an alcohol compound of formula II with a carboxylic acid of the formula R3 -COOH or its reactive derivative, an necessary, in the presence of a condensing agent (e.g. dicyclohexylcarbodiimide) or a base (e.g. triethylamine) in a solvent (e.g. THF) at -20 to +100 deg.C. The compound is effective against Spodoptera litura Fabricius, Nilaparvata lugens, Musca domestica vicina Macquart, cockroaches, Culex pipens pallens Coquillett, southern corn root worm, mites, etc.

Description

Detailed Description of the Invention

[0001]

OBJECT OF THE INVENTION The present invention relates to an ester compound, a pest control agent containing it as an active ingredient, and an intermediate for producing the same.

[0002]

The present inventors have conducted extensive studies to find a compound having an excellent pest control effect, and as a result,
It has been found that the ester compound represented by the following general formula (8) has excellent pest control activity, and in producing the ester compound, the alcohol compound represented by the following general formula (14) becomes a useful intermediate. It was found that the present invention has been completed. That is, the present invention provides a compound represented by the general formula

[Chemical 8][In the formula, R₁Represents a methyl group or a hydrogen atom, and R₂
Is C₁-C₆A haloalkyl group (eg, 2,2,2-to
Lifluoroethyl group, 2,2-difluoroethyl group,
Interfluoroethyl group, 2-fluoroethyl group, 3-fluoroethyl group
It may be substituted with a fluorine atom such as a luoropropyl group
I C₂-C_FourAlkyl group). R ₃Is Pirethro
Represents the residue of idic acid (portion excluding carboxyl group)
You ] The ester compound shown by (hereinafter, the compound of the present invention
Is written. ), A pest control agent containing it as an active ingredient and
And an intermediate for producing the same.

In the compound of the present invention, the residue of pyrethroid acid represented by R ₃ (portion excluding carboxyl group) is particularly a residue of carboxylic acid used as an active ingredient compound of an ester type pyrethroid insecticide. For example, but not limited to, general formula 9

[Chemical 9][Wherein, Z₁Represents a hydrogen atom or a methyl group. Z₂
Is C which may be substituted with hydrogen atom or halogen atom₁
-C₆Alkyl group (eg methyl group), halogen atom
C optionally substituted with₁-C₆Alkoxy group (eg
For example, C such as propoxy group and butoxy group₂-C_FiveArcoki
Si group, etc.), which may be substituted with a halogen atom (C₁
-C₆Alkoxy) methyl group, substituted with halogen atom
May be (C₁-C₆Alkoxy) ethyl group, halo
C optionally substituted with a gen atom ₂-C_FourAlkenyl
Oxy group (eg, allyloxy group, etc.), halogen atom
C optionally substituted with₂-C_FourAlkynyloxy group
(Eg propargyloxy group etc.)
May be replaced (C₂-C_FourAlkenyl) oxime
Cyl group (eg allyloxymethyl group etc.) or halo
Optionally substituted by a gen atom (C₂-C_FourAlkini
) Oxymethyl group (eg propargyloxymethyl
Group or the like, or

[Chemical 10] {In the formula, Z ₃ represents a hydrogen atom or a halogen atom.
T ₁ and T ₂ are the same or different and are a hydrogen atom, a halogen atom, or C ₁ which may be substituted with a halogen atom.
Represents a -C ₃ alkyl group, a cyano group, a phenyl group optionally substituted with a halogen atom, a (C ₁ -C ₄ alkoxy) carbonyl group optionally substituted with a halogen atom, or T ₁ and T ₂ and a group represented by (CH ₂ ) _n (where n represents an integer of 2 to 5) (ethylene group, trimethylene group, tetramethylene group, pentamethylene group). } Or a group represented by the formula:

[0004]

[Chemical 11] (In the formula, B represents an oxygen atom or a sulfur atom), or a group represented by the formula:

[Chemical 12] (In the formula, D represents a hydrogen atom or a halogen atom (eg, a fluorine atom), and G is a C ₁ -C ₆ alkyl group which may be substituted with a halogen atom (eg, a fluorine atom such as an ethyl group). An optionally substituted C ₁ -C ₃ alkyl group), a C ₃ -C ₅ cycloalkyl group (for example, a cyclopropyl group, etc.) or a phenyl group optionally substituted with a halogen atom). Alternatively, formula 13

[Chemical 13][In the formula, J is a halogen atom (eg, chlorine atom, fluorine
Atom, etc.), C optionally substituted with a halogen atom₁−
C₆Alkyl groups (eg trifluoromethyl group, dif
Substituted with a halogen atom)
May be C₁-C ₆Alkoxy groups (eg trifluoro
A romethoxy group, a difluoromethoxy group, etc.). ]
A group represented by

In the compound of the present invention, examples of the halogen atom include a fluorine atom, chlorine atom and bromine atom, examples of the alkyl group include a methyl group, ethyl group and propyl group, and examples of the alkenyl group include allyl. And the like. Examples of the alkynyl group include a propargyl group, and examples of the alkoxy include methoxy, ethoxy, propoxy and the like. In the compound of the present invention, C ₁ -C represented by R ₂
Of ₆ haloalkyl groups, C ₂ substituted with a fluorine atom
-C ₄ alkyl group is preferred, 2,2,2-trifluoroethyl group is particularly preferred. In the compound of the present invention, R
_{When 2} represents a secondary C ₁ -C ₆ haloalkyl group,
R ₁ is preferably a hydrogen atom, and when R ₂ represents a _primary C ₁ -C ₆ haloalkyl group, R ₁ is preferably a methyl group. In the compound of the present invention, preferred examples of the residue of pyrethroid represented by R ₃ (portion excluding the carboxyl group) are shown below.
And Q _{1 to} Q ₂₇ described in.

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

Embedded image [In the formula, R ₁ and R ₂ have the same meanings as described above. ]
And an alcohol compound represented by the general formula

Embedded image in R ₃ -COOH [wherein, R ₃ represents the same as defined above. ] The manufacturing method by making it react with the carboxylic acid shown by these or its reactive derivative. Examples of the reactive derivative of carboxylic acid include an acid halogen compound and an acid anhydride. The reaction is preferably carried out in an inert solvent in the presence of a suitable condensing agent or base, if necessary. Examples of the condensing agent used include dicyclohexylcarbodiimide (DCC) or 1-ethyl-3- (3-
Examples include dimethylaminopropyl) carbodiimide hydrochloride (WSC). Examples of the base used include organic bases such as triethylamine, pyridine, 4-dimethylaminopyridine and diisopropylethylamine. Usable solvents include hydrocarbons such as benzene, toluene and hexane, ethers such as diethyl ether and tetrahydrofuran,
Examples thereof include halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane. The reaction temperature is usually from -20 ° C to the boiling point of the solvent used in the reaction or 100 ° C.
The temperature can range from -5 ° C to the boiling point of the solvent used in the reaction or 100 ° C. Alcohol compounds of general formula 14 and general formula 1
The molar ratio of the carboxylic acid of 5 or the reactive derivative thereof to be used can be arbitrarily set, but it is advantageous to carry out at an equimolar ratio or a ratio close thereto. The condensing agent or base used as necessary may be used in an equimolar to excess amount ratio with respect to 1 mol of the alcohol compound of the general formula 14.
Desirably, the proportion is from equimolar to 5 molar. The reaction solution after completion of the reaction can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to obtain the desired compound of the present invention. If necessary, it may be further purified by usual operations such as chromatography, distillation and recrystallization.

The compound of the present invention may have stereoisomers (R, S) and geometric isomers (E, Z), but all stereoisomers and geometric isomers having pest control activity are included in the present invention. The body and mixtures thereof are included. The above production method A
In the above, by using an optically active raw material, the optically active compound of the present invention can be obtained while retaining stereoisomerism without racemization.

In the production method A, examples of the alcohol compound represented by the general formula 14 used as a raw material compound include the following compounds. (RS) -3- (2-Fluoroethyl) -2-methyl-
4-oxo-2-cyclopentenol (S) -3- (2,2,2-trifluoroethyl) -2
-Methyl-4-oxo-2-cyclopentenol (RS) -3- (3,3-difluoropropyl) -2-
Methyl-4-oxo-2-cyclopentenol (RS) -3- (pentafluoroethyl) -2-methyl-4-oxo-2-cyclopentenol (RS) -3- (2,2,2-tri Fluoroethyl)-
2-Methyl-4-oxo-2-cyclopentenol (RS) -3- (3,3,3-trifluoropyropyr)
2-Methyl-4-oxo-2-cyclopentenol (RS) -3- (2,2-difluoroethyl) -2-methyl-4-oxo-2-cyclopentenol (RS) -3- (2 -Chloroethyl) -2-methyl-4
-Oxo-2-cyclopentenol (RS) -3- (2-chloro-2,2-difluoroethyl) -2-methyl-4-oxo-2-cyclopentenol

The alcohol compound represented by the general formula 14 can be produced, for example, according to the method described in JP-A-57-67537. More specifically, for example, it can be produced by the method shown in Scheme 16 below.

Embedded image [In the formula, R ₁ and R ₂ have the same meanings as described above. The steps (i) and (ii) will be described below. Step (i): The ketocarboxylic acid compound represented by the formula [I] is added to the glyoxal derivative of the formula [II] and usually 1 in an alkaline aqueous solution or a mixed solvent of the ketocarboxylic acid compound and an inert solvent.
The reaction is carried out for 0 minutes to 48 hours, usually at 10 ° C to the boiling point of the solvent used or 100 ° C, preferably at 20 ° C to the boiling point of the solvent used or 100 ° C. The pH of the reaction solution is 7-9
It is advantageous to carry out the reaction in the range of As an inert solvent used as necessary, for example, diethyl ether,
Examples thereof include ethers such as tetrahydrofuran, halogenated hydrocarbons such as dichloromethane, and hydrocarbons such as benzene and toluene. The ketocarboxylic acid compound of the formula [I] and the glyoxal derivative of the formula [II] to be subjected to the reaction can be set at any molar ratio, but it is advantageous to carry out the reaction at an equimolar ratio or a molar ratio close thereto. Step (ii): The solvent is removed, and the residue is usually -5 in an alkaline aqueous solution of pH 10 or higher, preferably pH 13-14.
The reaction is carried out at a temperature of 0 ° C to 20 ° C, preferably -20 ° C to 5 ° C for usually 30 minutes to 48 hours. After completion of the reaction, the reaction solution can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound. If necessary, it can be further purified by operations such as chromatography and distillation.

The above-mentioned ketocarboxylic acid compound represented by the formula [I] can be produced, for example, by the method shown in the scheme 17 below.

[Chemical 17] Wherein, R and R 'are C ₁ -C ₄ same or different
Represents an alkyl group (eg, methyl group, ethyl group, etc.),
R ₂ has the same meaning as described above. ]

Next, the steps (a) to (e) will be described. The step (a) of hydrolyzing the ester represented by the formula [IV] to produce the carboxylic acid represented by the formula [V] will be described. Usually, water, methanol, ethanol, in a protic solvent such as ethylene glycol, for example, sodium hydroxide, alkali metal hydroxides such as potassium hydroxide, alkaline earth metal hydroxides such as barium hydroxide, A base such as a carbonate of an alkali metal such as potassium carbonate or sodium carbonate is usually used in an amount of 1 to 10 equivalents, preferably 1.2 to 5 equivalents, relative to the ester of the formula [IV], usually -10.
℃ ~ boiling point of the solvent used or 100 ℃, preferably 0 ℃
The reaction is usually performed at a temperature of -50 ° C for 30 minutes to 48 hours.
After completion of the reaction, the reaction solution can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound. If necessary, it can be further purified by an operation such as distillation.

The step (b) of halogenating the carboxylic acid represented by the formula [V] to produce the carboxylic acid halide represented by the formula [VI] will be described. Usually, the carboxylic acid of the formula [V] and the halogenating agent are usually added directly or with hexane,
The reaction is usually performed in a hydrocarbon such as pentane for 10 minutes to 48 hours. Examples of the halogenating agent to be used include inorganic chlorinated compounds such as phosphoryl chloride and thionyl chloride, and organic chlorinated compounds such as oxalic acid chloride. If necessary, pyridine, triethylamine, N, N- may be added to the reaction system.
A catalyst such as dimethylformamide or hexamethylphosphoric triamide may be added in a proportion of, for example, 0.01 to 1 mol with respect to 1 mol of the carboxylic acid of the formula [V]. The reaction temperature is usually from 0 ° C to the boiling point of the solvent used in the reaction or 1
It can be in the range of 50 ° C. The starting materials to be subjected to the reaction and the molar ratio of the halogenation can be set arbitrarily, but it is advantageous to carry out the reaction in an equimolar ratio or a ratio close thereto. After completion of the reaction, the reaction solution can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound. If necessary, it can be further purified by an operation such as distillation.

The step (c) of reacting the carboxylic acid halide represented by the formula [VI] with diethyl malonate to obtain the compound represented by the formula [VII] will be described. Usually, the formula [V
The carboxylic acid halide of [I] and diethyl malonate are reacted directly or in an inert solvent in the presence of an alcohol such as ethanol and methanol and a suitable metal. Examples of the metal to be used include alkaline earth metals such as magnesium and alkali metals such as lithium. Examples of the solvent used as needed include hydrocarbons such as benzene, xylene and toluene, and ethers such as diethyl ether, tetrahydrofuran and dioxane. The amounts of diethyl malonate, alcohol and metal to be used can be set arbitrarily with respect to the carboxylic acid halide of the formula [VI] used, but it is preferable to use 1.2 to 5 equivalents each. The reaction temperature is from -30 ° C to the boiling point of the solvent used in the reaction or 1
It can be in the range of 50 ° C. After completion of the reaction, the reaction solution can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound. If necessary, it can be further purified by operations such as chromatography, distillation and recrystallization.

The step (d) of hydrolyzing the compound represented by the formula [VII] and subsequently decarboxylating the compound to obtain the ketoester compound represented by the formula [VIII] will be described. When the reaction is carried out under basic conditions, usually, in a protic solvent such as water, methanol, ethanol, ethylene glycol or a mixed solvent thereof, for example, sodium hydroxide,
A ketoester compound of the formula [VII] in the presence of an alkali metal hydroxide such as potassium hydroxide, an alkaline earth metal hydroxide such as barium hydroxide, an alkali metal carbonate such as potassium carbonate or sodium carbonate, and the like. Is usually reacted at 0 ° C to the boiling point of the solvent used, preferably at a temperature of 30 ° C or higher for 10 minutes to 48 hours. The molar ratio of the raw material to be used for the reaction and the base can be set arbitrarily, but it is advantageous to carry out the reaction at an equimolar ratio or a ratio close thereto. When the reaction is performed under acidic conditions, paratoluenesulfonic acid, trifluoroacetic acid, hydrochloric acid, etc. in water or a mixed solvent of water and an alcohol such as ethanol, methanol or dioxane, ether such as tetrahydrofuran, etc. In the presence of the acid of formula (IV), the ketoester compound of the formula [IV] is usually used at 0 ° C to the boiling point of the solvent used, preferably at a temperature of 30 ° C or higher, usually for 10 minutes to 4
Allow to react for 8 hours. The molar ratio of the raw material and the acid used in the reaction can be set arbitrarily, but it is desirable to add them in a ratio of 0.0001 mol to 1 mo. After completion of the reaction, the reaction solution can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound. Chromatography if necessary,
It can be further purified by an operation such as distillation.

The step (e) of hydrolyzing the ketoester compound of the formula [VIII] to produce the ketocarboxylic acid compound of the formula [I] can be carried out, for example, in the same manner as the step (a).

Examples of pests for which the compound of the present invention exerts a controlling effect include the following. Hemiptera Pests Planthoppers such as the brown leafhopper, the brown planthopper, and the white-bellied planthopper, leafhoppers such as leafhoppers, leafhopper leafhoppers, leafhoppers, leafhoppers, stink bugs, whitefly insects, insect beetles, insect beetles, and insect beetles Long-spotted moth (Nikameichu), Red-spotted squid, White-spotted moth, etc., Spodoptera litura, Awayweed, Spodoptera litura and others, White butterfly such as cabbage butterfly, Yellow-spotted moth such as Coccinella palustris, Think moth,
Amothis genus ( Agrothis spp.), Heliothis spp., Such as leafminers, hemlocks, mosquitoes, cabbage moths, tamanaga moths, etc. Aedes mosquitoes such as Aedes albopictus, Anopheles mosquitoes such as Aedes albopictus, Chironomid species, house flies, house flies, house flies such as house flies, blow flies, flesh flies, seed flies, onion flies, fruit flies, fruit flies, fruit flies, fruit flies and fruit flies Coleoptera insects such as western corn rootworm, southern corn rootworm, scarab beetle such as western corn rootworm, scarab beetle, scarab beetle, weevils such as weevils, rice weevil, etc. Mushidamashi, mealworm such as red flour beetle, Kisujinomihamushi, Chrysomelidae such as corn rootworm, beetles such, Henosuepirakuna genera such as the beetle, Epilachna vigintioctopunctata (Henosu
epilacha spp.), flat beetle, long-tailed beetle, long-horned beetle, long-tailed beetle, blue-footed stag beetle, etc. Eye pests Ants, wasps, wasps, wasps and other wasps, etc.Orthoptera pests Kera, grasshoppers, etc.Heptoptera pests, human flea, etc.Lice pests Human lice, lice etc., pests, etc. Yamato termites, etc. Insects Ticks Mites, spider mites, spider mites, kanzawa mites, mandarin mites, apple mites, etc. Ticks Ocho-tick mites House dust mites, mite mites, dust mites, tick mites, etc. Cyst nematodes, root-knot nematode, and the like nematodes Matsuno THEY nematodes, Shin Galle nematodes, etc., etc.

When the compound of the present invention is used as an active ingredient of a pest controlling agent, it is usually mixed with a solid carrier, a liquid carrier, a gaseous carrier, a bait, or impregnated with a substrate such as mosquito coil or mat. If necessary, add surfactants and other auxiliaries for formulation to prepare oils, emulsions, wettable powders, flowable agents such as water suspensions / emulsions, granules, powders, aerosols, mosquito repellents. Heating and smoking agents such as incense sticks, electric mosquito mats and no mats, self-combustion type smoking agents / chemical reaction type smoking agents, heating smoking agents such as porous ceramic plate smoking agents, resin vaporizing agents, impregnated paper vaporizing agents Non-heated transpiration agent, etc., smoking agent such as fogging, UL
V formulation, poison bait, etc. are used. These formulations include
The compound of the present invention is usually used as an active ingredient in an amount of 0.001 by weight.
~ 95% content. Examples of solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talcs, ceramics, and other inorganic minerals (serisite, quartz, Sulfur, activated carbon, calcium carbonate,
Hydrated silica, etc., chemical fertilizers (ammonium sulfate, phosphorus ammonium, ammonium nitrate, urea,
Examples of the liquid carrier include water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, benzene, etc.). Toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane,
Kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, soybean oil, vegetable oils such as cottonseed oil, and the like, and a gaseous carrier, that is, a propellant, Examples thereof include CFC gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas and the like. Examples of the surfactant include alkyl sulfate salts, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenated products thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like. can give. Examples of auxiliary agents for formulations 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 alcohol). , Polyvinylpyrrolidone, polyacrylic acids, etc., and examples of the stabilizer include PAP (isopropyl acid phosphate) and BH.
T (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil , Surfactants, fatty acids or esters thereof, and the like. Examples of the base material of the mosquito coil include a mixture of vegetable raw powder such as wood powder and meal powder and a binder such as tab powder, starch and glutin. 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 base materials for self-burning smoke agents include nitrates, nitrites, guanidine salts, potassium chlorate, nitrocellulose, ethyl cellulose, wood powder, and other combustion heating agents, alkali metal salts, alkaline earth metal salts, and heavy chromium. Examples thereof include thermal decomposition stimulants such as acid salts and chromates, oxygen supplying agents such as potassium nitrate, combustion-supporting agents such as melamine and wheat starch, extenders such as diatomaceous earth, and binders such as synthetic pastes. Examples of the base material of the chemical reaction type smoke agent include alkali metal sulfides, polysulfides, hydrosulfides, hydrous salts, heat generating agents such as calcium oxide, carbonaceous substances, catalyst agents such as iron carbide and activated clay. , Organic foaming materials 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. As a base material for poison baits, for example, bait ingredients such as cereal flour, vegetable oil, sugar, crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaseletic acid, preservatives such as dehydroacetic acid, and pepper powder Examples include food inhibitors, cheese flavors, onion flavors, and peanut oil attractants. Formulations of flowable agents (suspension in water or emulsions in water) generally include 1-75% of the compound 0.5- 15% dispersant, 0.1-10% suspension aid (eg protection. Colloids and compounds that impart thixotropy), 0-10% of suitable auxiliaries (eg,
Antifoaming agent, rust preventive, stabilizer, spreading agent, permeation aid, antifreezing agent, antibacterial agent, antifungal agent, 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, etc. are used. Examples of the compound that imparts thixotropy 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 be used simultaneously with or without mixing with acaricide, nematicide, soil pest control agent, fungicide, herbicide, plant growth regulator, synergist, fertilizer and soil conditioner. Examples of the insecticide, nematicide and acaricide used include fenitrothion [O, O-dimethyl O- (3-methyl-4-nitrophenyl) phosphorothioate] and fenthion [O, O-dimethyl O- (3 -Methyl-4-
(Methylthio) phenyl) phosphorothioate], diazinon [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 phosphorothioate], DDV
P [2,2-dichlorovinyl dimethyl phosphate],
Sulprophos [O-ethyl O-4- (methylthio) phenyl S-propyl phosphorodithioate], cyanophos [O-4-cyanophenyl O, O-dimethylphosphorothioate], dioxabenzophos [2-methoxy-4H-1] , 3,2-Benzodioxaphosphinin-2
-Sulfide], dimethoate [O, O-dimethyl-S
-(N-methylcarbamoylmethyl) dithiophosphate], fentoate [ethyl 2-dimethoxyphosphinothioylthio (phenyl) acetate], malathion [diethyl (dimethoxyphosphinothioylthio) succinate], trichlorfon [dimethyl 2,2,2,2] Two
-Trichloro-1-hydroxyethylphosphonate],
Azinphos-methyl [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], ethione [O, O,
O ', O'-tetraethyl S, S'-methylene bis (phosphorodithioate)] and other organic phosphorus compounds, B
PMC (2-sec-butylphenylmethylcarbamate), benfuracarb [ethyl N- (2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N-isopropyl-
β-alaninate], propoxur [2-isopropoxyphenyl N-methylcarbamate], carbosulfan [2,3-dihydro-2,2-dimethyl-7-benzo [b] furanyl N-dibutylaminothio-N-methyl Carbamate], carbaryl [1-naphthyl-N-methylcarbamate], Methomyl [S-methyl-N-
[(Methylcarbamoyl) oxy] thioacetimidate], Ethiophencarb [2- (ethylthiomethyl)]
Phenylmethylcarbamate], aldicarb [2-methyl-2- (methylthio) propionaldehyde O-
Methylcarbamoyloxy], oxamyl [N, N-dimethyl-2-methylcarbamoyloxyimino-2-]
(Methylthio) acetamide], phenothiocarb [S-
Carbamate compounds such as 4-phenoxybutyl) -N, N-dimethylthiocarbamate, etofenprox [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], phenpropatorin [(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 [(R
S) -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 (1
R) -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), bifensulin (2-methylbiphenyl-3-ylmethyl) (Z)-(1RS) -ci
s-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
{(1′RS) (1 ′, 2 ′, 2 ′, 2′-tetrabromoethyl)}-2,2-dimethylcyclopropanecarboxylic acid (S) -α-cyano-3-phenoxybenzyl ester], silafluofene [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], acrinathrin [(S) -α-cyano-3]
-Phenoxybenzyl (1R-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, Two
-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-terahydrophthalimidomethyl (1RS) -cis, trans-chrysanthemate], Allethrin [(RS) -3-allyl-]
2-methyl-4-oxocyclopent-2-enyl (1
RS) -cis, trans-chrysanthemate], Praresulin [(S) -2-methyl-4-oxo-3- (2-
Propynyl) cyclopent-2-enyl (1R) -cis, trans-chrysanthemate], empensulin [(RS) -1-ethynyl-2-methyl-2-pentenyl (1R) -cis, trans-chrysanthemate],
Imiprothrin [2,5-dioxo-3- (prop-2
-Inyl) imidazolidin-1-ylmethyl (1R)
-Cis, trans-2,2-dimethyl-3- (2-methylprop-1-enyl) cyclopropanecarboxylate], d-flamethrin [5- (2-propynyl) furfuryl (1R) -cis, trans-chrysante Mart], 5- (2-propynyl) furfuryl 2,2
Pyrethroid compounds such as 3,3-tetramethylcyclopropanecarboxylate, buprofezin (2-tert-
Butyrimino-3-isopropyl-5-phenyl-1,
Thiadiazine derivatives such as 3,5-thiadiazin-4-one), nitroimidazolidine derivatives such as imidacloprid (1- (6-chloro-3-pyridylmethyl) -N-nitroimidazolidine-2-indeneamine], cartap (S, S ′) -(2-dimethylaminotrimethylene)
Bis (thiocarbamate)], thiocyclam [N, N-
Nereistoxin derivatives such as dimethyl-1,2,3-trithian-5-ylamine], bensultap [S, S′-2-dimethylaminotrimethylene di (benzenethiosulfonate)], N-cyano-N ′. -Methyl-
N-cyanoamidine derivatives such as N '-(6-chloro-3-pyridylmethyl) acetamidine, endosulfan [6,7,8,9,10,10-hexachloro-1,
5,5a, 6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine oxide], γ-BHC (1,2,3,4,5,6-hexachlorocyclohexane ], 1,1-bis (chlorophenyl) -2,2,2-trichloroethanol and other chlorinated hydrocarbon compounds, chlorfluazuron [1- (3,5-dichloro-4- (3-chloro-5- Trifluoromethylpyridin-2-yloxy) phenyl) -3- (2,6-
Difluorobenzoyl) urea], teflubenzuron [1- (3,5-dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea], fluphenoxuron [1- (4- (2- Chloro-
4-trifluoromethylphenoxy) -2-fluorophenyl] -3- (2,6-difluorobenzoyl) urea] and other benzoylphenylurea compounds, amitraz [N, N ′ [(methylimino) dimethylidene] di-
2,4-xylidine], chlordimeform [N '-(4
-Chloro-2-methylphenyl) -N, N-dimethylmethinimidamide] and the like, formamidine derivatives, diafenthiuron [N- (2,6-diisopropyl-4-phenoxyphenyl) -N'-tert-butyl Carbodiimide]
Derivatives such as thiourea, promopropylate [isopropyl 4,4'-dibromobenzilate], tetradiphone [4-chlorophenyl 2,4,5-trichlorophenyl sulfone], quinomethionate [S, S-6-methylquinoxaline-2, 3-diyldithiocarbonate],
Propargate [2- (4-tert-butylphenoxy)
Cyclohexylprop-2-yl sulfite],
Fenbutatin oxide [bis [tris (2-methyl-2-phenylpropyl) tin] oxide], hexithiazox [(4RS, 5RS) -5- (4-chlorophenyl) -N-chlorohexyl-4-methyl-2- Oxo-1,3-thiazolidine-3-carboxamide],
Clofentedine [3,6-bis (2-chlorophenyl) -1,2,4,5-tetrazine, pyridathiobene [2-tert-butyl-5- (4-tert-butylbenzylthio) -4-chloropyridazine- 3 (2H) -on],
Fenpyroximate [tert-butyl (E) -4-
[(1,3-Dimethyl-5-phenoxypyrazole-4
-Yl) methyleneaminotoxymethyl] benzoate], debufenpyrad [N-4-tert-butylbenzyl) -4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide], polynactin complex [tetranactin, dinactin, Trinactin], milbemectin, avermectin, ivermectin, azadirachtin [AZAD], pyrimidifen [5-chloro-
N- [2- {4- (2-ethoxyethyl) -2,3-dimethylphenoxy} ethyl] -6-ethylpyrimidine-
4-amine, fipronil [1H-pyrazole-3-carbonitrile-5-amino-1- {2,6-dichloro-
4- (trifluoromethyl) phenyl} -4-{(trifluoromethyl) sulfinyl}] and other phenylpyrazole compounds, methoxadiazone [5-methoxy-3-
(2-methoxyphenyl) -1,3,4-oxadiazol-2 (3H) -one] and the like.

When the compound of the present invention is used as an active ingredient of an agricultural pest control agent, the application amount is usually 5 to 500 g per 10 ares, and the emulsion, wettable powder, flowable agent, etc. are diluted with water and applied. , Its application concentration is 0.1-1000
It is ppm, and granules, powders, etc. are applied as they are without any dilution. When it is used as an active ingredient of a pest control agent for household and epidemic prevention, emulsions, wettable powders, flowable agents, etc. are diluted with water to 0.1 to 1000ppm and then applied, and oils, aerosols, fumigants, fumes are used. Agent, transpiration agent, fuming agent, U
LV agents, poison baits, etc. are applied as they are. The application amount and application concentration of these are all the types of preparations, application time,
It depends on the situation such as application place, application method, kind of pest, degree of damage, etc., and can be increased or decreased without being concerned with the above range.

[0020]

EXAMPLES The present invention will be described in more detail below with reference to production examples, formulation examples, test examples, etc., but the present invention is not limited to these examples. First, production examples of the compound of the present invention will be shown. Production Example 1 (RS) -2-methyl-3- (2,2,2-trifluoroethyl) -4-oxocyclopent-2-ene-1-
To a mixed solution of all 300 mg, 2,6-di-tert-butyl-4-methylphenol 5 mg, pyridine 185 mg, 4-dimethylaminopyridine 5 mg and dry tetrahydrofuran 8 ml, under ice-cooling, (1R) -trans-3- ( Two
After adding 422 mg of 2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylic acid chloride, the reaction was continued at room temperature for 8 hours. Then, 10 ml of 10% aqueous ammonia solution was added to the reaction solution, which was vigorously stirred for 2 hours. The reaction solution was extracted three times with diethyl ether, the ether layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography (developing solvent: 0.1% 2,6-di-tert-
Subject to an n-hexane / ethyl acetate mixture containing butyl-4-methylphenol (30: 1) and target (RS) -2-methyl-3- (2,2,2-trifluoroethyl)- 4-oxo-2-cyclopenten-1-yl (1R) -trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate (inventive compound 5) 460 mg (yield 77%) Got n _D ²⁵ 1.4915 ¹ H-NMR (CDCl ₃ , TMS internal standard) δ value (ppm) 1.21 (m, 3H), 1.35 (m, 3)
H), 1.63 (m, 1H), 2.12 (d, 3H), 2.3
5 (m, 2H), 2.76 (m, 1H), 3.12 (q, 2
H), 5.62 (m, 1H), 5.76 (brd, 0.5)
H), 5.85 (brd, 0.5H)

Production Example 2 (RS) -2-Methyl-3- (2,2,2-trifluoro)
Rhoethyl) -4-oxocyclopent-2-ene-1-
All 300 mg, 2,6-di-tert-butyl-4-meth
Luphenol 5mg, Pyridine 185mg, 4-Dimethyla
5 mg of minopyridine and 8 ml of dry tetrahydrofuran
2,2,3,3-tetramethylsilane was added to the mixed solution under ice cooling.
Clopropanecarboxylic acid chloride (70% (w / w)
Ruene solution) 425 mg was added dropwise and the reaction was continued at room temperature for 6 hours.
I did. After that, 10 ml of 10% aqueous ammonia solution is added to the reaction solution.
Was added and the mixture was vigorously stirred for 2 hours. Add the reaction solution to diethyl ether.
Extract three times with ether, combine the ether layers, and add saturated saline.
Wash and dry over anhydrous magnesium sulfate, then remove the solvent under reduced pressure.
Was distilled off. Silica gel column chromatography of the residue
-(Developing solvent: 0.1% 2,6-di-tert-butyl-4
N-hexane / ethyl acetate containing methylphenol
(RS) -2, which is the target (RS) -2.
-Methyl-3- (2,2,2-trifluoroethyl)-
4-oxo-2-cyclopenten-1-yl 2,2,2
3,3-tetramethylcyclopropanecarboxylate
(Invention compound 9) 275 mg (yield 56%) was obtained. n_D ^{twenty five} 1.4621¹ H-NMR (CDCl₃, TMS internal standard) δ value (ppm) 1.23 (m, 13H), 2.11 (s,
3H), 2.32 (dd, 1H), 2.92 (dd, 1)
H), 3.10 (q, 2H), 5.73 (brd, 1H) ¹⁹ F-NMR (CDCl₃, CCl₃F internal standard) δ value (ppm) −64.95 (t, 3F)

Production Example 3 (RS) -2-Methyl-3- (2,2,2-trifluoroethyl) -4-oxocyclopent-2-ene-1-
All 300 mg, 2,6-di-tert-butyl-4-methylphenol 5 mg, pyridine 183 mg and toluene 7
ml mixed solution under ice-cooling (1R) -trans-2,2-
After adding 270 mg of dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid chloride, the reaction was continued at room temperature for 8 hours. The reaction solution was poured into ice-cooled 5% citric acid and extracted with diethyl ether three times. The ether layers were combined, washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine,
After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue is subjected to silica gel chromatography (developing solvent:
N-Hexane / ethyl acetate mixture containing 0.1% 2,6-di-tert-butyl-4-methylphenol (3
0: 1)), and the target (RS) -2-methyl-
4-oxo-3- (2,2,2-trifluoroethyl)
2-Cyclopenten-1-yl (1R) -trans-2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate (inventive compound 1) 330 mg (yield 66%) was obtained. It was n _D ²² 1.5185 ¹ H-NMR (CDCl ₃ , TMS internal standard) δ value (ppm) 1.17 (m, 3H), 1.39 (m, 3)
H), 1.42 (m, 1H), 1.70 (m, 6H), 2.1
2 (m, 4H), 2.35 (m, 1H), 2.92 (m, 1)
H), 3.10 (q, 2H), 4.91 (m, 1H), 5.7
1 (brd, 0.5H), 5.82 (brd, 0.5H) ¹⁹ F-NMR (CDCl ₃ , CCl ₃ F internal standard) δ value (ppm) −64.93 (t, 3H)

Production Example 4 (RS) -2-Methyl-3- (2,2,2-trifluoroethyl) -4-oxocyclopent-2-ene-1-
All 300 mg, 2,6-di-tert-butyl-4-methylphenol 5 mg, pyridine 178 mg, 4-dimethylaminopyridine 5 mg and dry tetrahydrofuran 10 ml.
(2S) -2- (4-chlorophenyl) -3-methylbutanoic acid chloride (400 mg) was added dropwise to the mixed solution of (3) under ice cooling, and the reaction was continued at room temperature for 6 hours. Then, add 10 to the reaction mixture.
10% aqueous ammonia solution was added, and the mixture was vigorously stirred for 2 hours. The reaction solution was extracted three times with diethyl ether, the ether layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography (developing solvent: 0.1% 2,
Subject to a mixture of n-hexane / ethyl acetate (30: 1) containing 6-di-tert-butyl-4-methylphenol to give the desired (RS) -2-methyl-3- (2,2,2).
2-Trifluoroethyl) -4-oxo-2-cyclopenten-1-yl (2S) -2- (4-chlorophenyl) -3-methylbutanoic acid carboxylate (inventive compound 16) 450 mg (yield 78%) Got n _D ²⁴ 1.4989 ¹ H-NMR (CDCl ₃ , TMS internal standard) δ value (ppm) 0.71 (m, 3H), 1.09 (m, 3)
H), 1.95 (d, 3H), 2.28 (m, 2H), 3.0
2 (m, 3H), 3.20 (d, 1H), 5.78 (m, 1
H), 7.28 (m, 4H) ¹⁹ F-NMR-64.91 (t, 3F)

Production Example 5 (RS) -2-Methyl-3- (2,2,2-trifluoroethyl) -4-oxocyclopent-2-ene-1-
All 300 mg, 2,6-di-tert-butyl-4-methylphenol 5 mg, pyridine 178 mg, 4-dimethylaminopyridine 5 mg and dry tetrahydrofuran 10 ml.
(2S) -2- (4-Fluorophenyl) -3-methylbutanoic acid chloride (368 mg) was added dropwise to the mixed solution of (3) under ice cooling, and the reaction was continued at room temperature for 6 hours. Then add 1 to the reaction mixture.
10 ml of 0% aqueous ammonia solution was added, and the mixture was vigorously stirred for 2 hours. The reaction solution was extracted three times with diethyl ether, the ether layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography (developing solvent: n-hexane / ethyl acetate mixture (30: 1) containing 0.1% 2,6-di-tert-butyl-4-methylphenol) to give the desired compound. (RS) -2-methyl-3- (2,
2,2-Trifluoroethyl) -4-oxo-2-cyclopenten-1-yl (2S) -2- (4-fluorophenyl) -3-methylbutanoic acid carboxylate (inventive compound 70) 400 mg (yield 73 %) Was obtained. n _D ²⁴ 1.4819 ¹ H-NMR (CDCl ₃ , TMS internal standard) δ value (ppm) 0.78 (m, 3H), 1.09 (m, 3)
H), 1.95 (d, 3H), 2.81 (m, 2H), 3.0
1 (m, 3H), 3.20 (d, 1H), 5.76 (m, 1
H), 7.02 (m, 2H), 7.32 (m, 2H) ¹⁹ F-NMR (CDCl ₃ , CCl ₃ F internal standard) -115.34 (s, 1F), -64.91 (t , 3F)

Examples of the compounds of the present invention are shown in Table 1 together with the compound numbers.
~ Shown in Table 4. (Individual substituents of the compound represented by the general formula: are shown.) In Tables 1 to 4, Q _{1 to} Q ₂₇ represented by R ₃ are the same as those shown in the chemical formulas 18 and 19.

[Chemical 18]

[0026]

[Chemical 19]

[0027]

[Table 1]

[Table 2]

[0028]

[Table 3]

[Table 4] Next, some physical properties of the compounds of the present invention will be shown. Compound number 1 n _D ²² 1.5185 5 n _D ²⁵ 1.4915 9 n _D ²⁵ 1.4621 16 n _D ²² 1.4989 70 n _D ²⁴ 1.4819

Next, production examples of the alcohol compound represented by the general formula 14 will be shown. Production Example of Intermediate To 98.8 g of ethyl 4,4,4-trifluorobutyryl acetate, 250 ml of 10% aqueous sodium hydroxide solution was added, and the mixture was vigorously stirred for 12 hours. 10% in the reaction solution
After adding an aqueous solution of sulfuric acid to adjust the pH to 7.5, 250 ml of toluene, 2.86 g of sodium hydrogen carbonate and 6.43 g of hydrosulfite were added under a nitrogen stream and heated to 37 ° C. 90 g of methylglyoxal was added dropwise thereto over 1 hour, and the reaction was continued for 12 hours. Sodium chloride (50 g) was added to the reaction mixture, and the mixture was extracted 3 times with ethyl acetate. Combine the ethyl acetate layers,
After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. To the residue, under ice cooling, 5% aqueous sodium hydroxide solution 45
0 ml was added and the mixture was vigorously stirred for 5 hours. The reaction mixture was adjusted to pH 7.3 with 10% aqueous hydrochloric acid and extracted 3 times with ethyl acetate. The ethyl acetate layers were combined and dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was distilled off under reduced pressure to obtain the desired (RS) -2-methyl-3- (2,2,2- Trifluoroethyl) -4-oxocyclopent-2-en-1-ol (bp 100-133 ° C, 0.52 mH
g) 45 g (yield 50%) was obtained. ¹ H-NMR (CDCl ₃ , TMS internal standard) δ value (ppm): 2.19 (s, 3H), 2.35 (dd,
1H), 2.85 (dd, 1H), 3.08 (q, 2H),
4.82 (br, 1H) ¹⁹ F-NMR (CDCl ₃ , CCl ₃ F internal standard) δ value (ppm): −65.1 (t, 3F)

Next, the compounds [V]
An example of production of [VIII] is shown. Reference Production Example (1) Production Example of Compound (V) 160 g of ethyl 4,4,4-trifluorobutyrate
To the above, a mixed solution of 123 g of potassium hydroxide, 900 ml of methanol and 80 ml of water was added under ice cooling, and then the mixture was stirred at room temperature for 1 hour.
The reaction was continued for 2 hours. The reaction solution was concentrated under reduced pressure, and water and diethyl ether were added to the obtained residue to separate the layers. The ether layer was extracted once with water, combined with the previously separated aqueous layer, and an ice-cooled 10% aqueous hydrochloric acid solution was added to adjust the pH to about 1, and then extracted three times with diethyl ether. The ether layers were combined, washed twice with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain the desired 4,4,4
131 g of trifluorobutyric acid (yield 98
%) Was obtained. ¹ H-NMR (CDCl ₃ , TMS internal standard) δ value (ppm): 2.52 (m, 2H), 2.67 (t, 2)
H) (2) Production example of compound (VI) 4,4,4-trifluorobutyric acid 131 g
Oxalyl chloride 101 in a mixture of 1 liter and pentane.
ml and dimethylformamide 0.1 ml were added and the mixture was heated under reflux for 3 hours. Distill the reaction solution at atmospheric pressure to obtain the desired
112 g of 4,4-trifluorobutyryl chloride (b.
p103 ° C., 760 mHg) (yield 76%) was obtained.

(3) Production Example of Compound (VII) Magnesium (cutting) 20.35 g and ethanol 148 ml
0.1 ml of carbon tetrachloride was added to the above mixture and heated to 55 ° C. To this, a mixed solution of 197 ml of ethanol, 700 ml of diethyl ether and 168 g of diethyl malonate was added dropwise over 1 hour. After 2 hours, the reaction solution was cooled to −5 ° C. under a nitrogen stream, 112 g of 4,4,4-trifluorobutyryl chloride was added, the temperature was returned to ambient temperature over 1 hour, and the reaction was continued for 12 hours. It was The reaction mixture was poured into ice-cooled 5% hydrochloric acid aqueous solution and extracted with diethyl ether three times. The ether layers were combined and washed twice with saturated saline,
After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was distilled off under reduced pressure to obtain the target diethyl 4,4,4-trifluorobutyryl malonate (b · p125 to 13).
179 g (yield 90%) was obtained at 4 ° C. and 15 mHg. ¹ H-NMR (CDCl ₃ , TMS internal standard) δ value (ppm): 1.32 (t, 3H), 2.50 (m, 2)
H), 2.95 (t, 2H), 4.29 (q, 2H), 4.5
0 (s, 1H) (4) Production Example of Compound (VIII) Diethyl 4,4,4-trifluorobutyrylmalonate 1
79 g, water 260 ml, paratoluene sulfonic acid 322 mg
The mixture of 1 was vigorously stirred for 6 hours while heating under reflux.
The reaction mixture was poured into saturated aqueous sodium hydrogen carbonate, and the mixture was diluted with diethyl ether to 3 times.
Extracted times. The ether layers were combined and washed with saturated saline,
After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was distilled off under reduced pressure to obtain the desired ethyl 4,4,4
-Trifluorobutyryl acetate (b-p93-97
98.8 g (yield 74%) was obtained. ¹ H-NMR (CDCl ₃ , TMS internal standard) δ value (ppm): 1.28 (t, 3H), 2.45 (m, 2)
H), 2.96 (t, 2H), 3.48 (s, 2H), 4.2
2 (q, 2H)

Next, formulation examples are shown. The parts are parts by weight, and the compounds of the present invention are represented by the compound numbers shown in Tables 1 to 4. Formulation Example 1 Emulsion 20 parts of each of the compounds (1) to (74) are dissolved in 65 parts of xylene, 15 parts of an emulsifier Sorpol 3005X (registered trademark of Toho Kagaku Co., Ltd.) is added, and well mixed with stirring to prepare a 20% emulsion To get Formulation Example 2 Wettable powder Solupol 3005X to 40 parts of each of the compounds (1) to (74)
Add 5 parts (above), mix well, and use Carplex #
32 parts of 80 (Shionogi registered trademark, synthetic silicon oxide hydroxide fine powder) and 23 parts of 300 mesh diatomaceous earth are added and mixed by stirring with a juice mixer to obtain each 40% wettable powder. Formulation Example 3 Granules 1.5 parts of each of Compounds (1) to (74) and AGSORBLVM-MS
24/48 (fired montmorillonite manufactured by OIL DRI,
98.5 parts of granular carrier having a particle size of 24 to 48 mesh) and well mixed to obtain each 1.5% granule. Formulation Example 4 Microcapsules After mixing 10 parts of each of the compounds (1) to (74), 10 parts of phenylxylylethane and 0.5 part of Sumidule L-75 (tolylene diisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.), It is added to 20% of 10% aqueous solution of gum arabic and stirred with a homomixer to obtain an emulsion having an average particle size of 20 μm. Next, 2 parts of ethylene glycol was added thereto, and the mixture was further reacted in a warm bath at 60 ° C. for 24 hours to obtain a microcapsule chiller. On the other hand, Zangsangam 0.
2 parts and 1.0 part of Veegum R (aluminum magnesium silicate manufactured by Sanyo Kasei) are dispersed in 56.3 parts of ion-exchanged water to obtain a thickener solution. Micro capsule thriller 4 above
2.5 parts and 57.5 parts thickener solution are mixed to give 10 parts each.
% To obtain microcapsules. Formulation Example 5 Flowable Agent After mixing 10 parts of each of the compounds (1) to (74) and 10 parts of phenylxylylethane, the mixture was added to 20 parts of a 10% aqueous solution of polyethylene glycol and stirred with a homomixer to give an average particle size. An emulsion with a diameter of 3 μm is obtained. On the other hand, 0.2 parts of xanthan gum and 1.0 part of Veegum R (aluminum magnesium silicate manufactured by Sanyo Kasei) are dispersed in 58.8 parts of ion-exchanged water to obtain a thickener solution. The emulsion 40
Parts and 60 parts thickener solution to mix to obtain each 10% flowable agent. Formulation Example 6 Powder 5 parts of each of Compounds (1) to (74) is added to Carplex # 8.
3 parts of 0 (the above), 0.3 parts of PAP and 91.7 parts of 300 mesh talc are added and mixed by stirring with a juice mixer to obtain each 5% powder. Formulation Example 7 Oil agent 0.1 parts of each of the compounds (1) to (74) was added to dichloromethane 5
Dissolved in 9 parts of deodorized kerosene,
Obtain 1.0% oil. Formulation Example 8 Oily aerosol Compounds (1) to (74) (1 part each), dichloromethane (5 parts) and deodorizing kerosene (34 parts) are mixed and dissolved, the mixture is filled in an aerosol container, and a valve portion is attached, and then a propellant is passed through the valve portion. 60 parts of (liquefied petroleum gas) is charged under pressure to obtain each oil-based aerosol. Formulation Example 9 Aqueous aerosol Compounds (1) to (74) each containing 0.6 part, xylene 5 parts, deodorizing kerosene, 3.4 parts and an emulsifier {Atmos 300 (registered trade name of Atlas Chemical Co.)} 1 part are mixed and dissolved. And 50 parts of pure water are filled in an aerosol container, a valve portion is attached, and 40 parts of a propellant (liquefied petroleum gas) is charged under pressure through the valve portion to obtain each aqueous aerosol. Formulation Example 10 Mosquito coil Incense 0.3 parts of each of the compounds (1) to (74) is dissolved in 20 ml of acetone, and a carrier for mosquito coil (4: tab powder: lees powder, wood powder:
Mix in a ratio of 3: 3) 99.7 g with stirring and mixing,
120 ml of water was added, and the mixture was thoroughly kneaded, molded and dried to obtain each mosquito coil. Formulation Example 11 Electric Mosquito Repellent Mat Acetone was added to 0.8 g of each of the compounds (1) to (74) and 0.4 g of piperonyl butoxide, and dissolved to give a total of 1
Make up to 0 ml. 0.5 ml of this solution is 2.5 cm x 1.5 cm, thickness
Each of the electric mosquito repellent mat agents is obtained by uniformly impregnating a 0.3 cm base material for electric mat (solidified fibril of a mixture of cotton linter and pulp into a plate). Formulation Example 12 Liquid Electric Mosquito Repellent Liquid Absorbent core (inorganic powder) in which 3 parts of each of Compounds (1) to (74) was dissolved in 97 parts of deodorized kerosene, placed in a vinyl chloride container, and the upper part of which was heated by a heater. Each body is hardened with a binder and sintered) and inserted to obtain each liquid electric mosquito repellent. Formulation Example 13 Heat Smoke Agent Compounds (1) to (74) (100 mg each) are dissolved in an appropriate amount of acetone and impregnated into a 4.0 cm × 4.0 cm, 1.2 cm thick porous ceramic plate, Get a heated smoker. Formulation Example 14 Normal temperature volatilizer 100 μg of each of the compounds (1) to (74) is dissolved in an appropriate amount of acetone, and uniformly applied on a filter paper of 2 cm × 2 cm and thickness of 0.3 mm, and then air-dried with acetone, respectively. To obtain a room temperature transpiration agent. Formulation Example 15 Mite-proof sheet Each of the compounds (1) to (74) is dropped and impregnated into a filter paper at 1 g per 1 m ² , and acetone is air-dried to obtain each mite-proof sheet.

Next, it will be shown by 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 4, and the compounds used for comparison and control ((RS) form on the alcohol side and (1R) -cis, trans form on the acid side) are represented by the compound symbols in Table 5. Show.

[Table 5]

Test Example 1 Insecticidal test against Larvae of Spodoptera litura L. 13 g of artificial emulsion for Spodoptera litura that was prepared by diluting 2 ml of a water-diluted solution (500 ppm) of the emulsion of the test compound obtained according to Formulation Example 1 in a polyethylene cup with a diameter of 11 cm. Soaked in the feed. Among them, Hasmonyoto 4th instar larva, 1
0 animals were released, and their life and death were investigated 6 days later, and the mortality rate was calculated. Table 6 shows the results.

[Table 6] Test Example 2 Insecticidal test against larvae of brown planthoppers Rice stalks (about 5 cm in length) were immersed in a diluted solution (500 ppm) of the emulsion of the test compound obtained according to Formulation Example 1 for 1 minute. After air-drying, put rice stalks in a 5.5 cm diameter polyethylene cup lined with 5.5 cm diameter filter paper containing 1 ml of water, and release about 30 larvae of the brown planthopper into the cup. investigated. The criteria for effect evaluation are: a: No live insects are observed. b: Five or less surviving insects are recognized. c: 〃 6 or more are allowed. And The results are shown in Table 7.

[Table 7]

Test Example 3 Insecticidal test against housefly A polyethylene cup having a diameter of 5.5 cm is covered with a filter paper of the same size, and the emulsion of the test compound obtained according to Formulation Example 1 is diluted with water (500 ppm). 0.7 ml was dropped on the filter paper, and about 30 mg of sucrose was uniformly added as a bait. Ten adult females of the housefly of low pyrethroid susceptibility were released therein, the lid was placed on the lid, and one day later, the life and death thereof were examined to determine the mortality rate. The results are shown in Table 8.

[Table 8] Test Example 4 Ten adult German cockroaches (5 males and 5 females) were released in a polyethylene cup with a diameter of 9 cm, which was thinly coated with vaseline, and covered with a 16-mesh nylon gauze. The inner diameter was 10 cm and the height was 37 cm. It was installed at the bottom of the cylinder. 0.1 of the compound of the present invention obtained in Formulation Example 7
% (W / w) oil solution (0.6 ml each) was directly sprayed from the upper end of the cylinder at a pressure of 0.6 atm with a spray gun. After 5 minutes, knockdown insects were observed and the knockdown insect rate was calculated. The results are shown in Table 9.

[Table 9]

[0036] and the release, the 10 animals Culex female adults in the glass chamber of Test Example 5 70cm cubic (0.34 m ^3). In this glass chamber, 0.3% of the compound of the present invention obtained according to Preparation Example 10 was added.
(W / w) 1.0 g of mosquito coil was ignited at both ends. After 8.5 minutes, the knockdown rate of the test insects was investigated. The results are shown in Table 1.
0 is shown.

[Table 10] Test Example 6 Insecticidal test against Culex pipiens A test compound was made into an emulsion according to Formulation Example 1, diluted with water, and 0.7 ml of the solution was added to 100 ml of ion-exchanged water (concentration of active ingredient: 3.5 ppm). 20 dead larvae of Culex pipiens were released in it, and the mortality rate after 1 day was investigated. The criteria for effect evaluation are as follows: a: mortality rate of 90% or more b: mortality rate of 10% or more and less than 90% c: mortality rate of less than 10%. The results are shown in Table 11.

[Table 11]

Test Example 7 Insecticidal test against Southern corn rootworm larvae A polyethylene cup having a diameter of 5.5 cm was covered with a filter paper of the same size, and the emulsion of the test compound obtained according to Formulation Example 1 was diluted with water. 1 ml of the liquid (50 ppm) was dropped on the filter paper. Approximately 30 eggs of Southern corn mutworm were placed on this filter paper, and one corn sprout was put as a bait. After 8 days, the survival of dead larvae was investigated. The criteria for effect evaluation were as follows: a: 100% mortality rate b: 99-90% mortality rate c: less than 90% mortality rate. The results are shown in Table 12.

[Table 12] Test Example 8 0.25% of the test compound was placed on an aluminum dish with a diameter of 7 cm at the bottom.
0.64 ml of (w / v) acetone diluted solution was added dropwise, and acetone was air-dried. Polyethylene cup (diameter 9 cm, height 4.5c
20 adult female CSMA type houseflies were released in m), and a 16-mesh nylon net was placed on the upper part of the insects to prevent the insects from directly contacting the drug-treated surface. Put this cup upside down,
It was placed on the above-mentioned aluminum dish, and after 60 minutes at 25 ° C., knockdown insects were counted and the mortality rate was calculated. The results are shown in Table 13.

[Table 13]

Test Example 9 A mite-proof sheet prepared according to Formulation Example 15 was used, and the diameter was 4 cm.
Cut into circles, and on the surface of the filter paper, Dermatopha
About 50 goides farinae ) were released , and one day later, the number of mites trapped in the sticky substance applied to the edge of the filter paper to prevent life and death and escape was observed. The total of dead insects and trapped insects was regarded as effective insect control, and the control rate was calculated. The results are shown in Table 14.

[Table 14]

[0039]

The compounds of the present invention have excellent pest control activity.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 69/747 H 9546-4H 69/757 A 9546-4H 255/31 C07D 307/58 333/32 (72) Inventor Tagao Ishiwata 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd. (72) Inventor Toru Tsuchiya 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd. (72) Inventor Mikako Nakamachi 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd.

Claims (4)

[Claims] 1. A compound represented by the general formula: [In the formula, R ₁ represents a methyl group or a hydrogen atom, and R ₂
Represents a C ₁ -C ₆ haloalkyl group. R ₃ represents a residue of pyrethroid acid (a portion excluding a carboxyl group). ] The ester compound shown by these. 2. R₃Is the general formula:[Wherein, Z₁Represents a hydrogen atom or a methyl group. Z₂
Is C which may be substituted with hydrogen atom or halogen atom₁
-C₆May be substituted with an alkyl group or halogen atom
I C₁-C₆Alkoxy group, substituted with halogen atom
May be (C₁-C₆Alkoxy) methyl group, halogen
Optionally substituted with a hydrogen atom (C₁-C ₆Arcoki
Si) Ethyl group, C optionally substituted with a halogen atom
₂-C_FourAlkenyloxy group, substituted with halogen atom
May be C₂-C_FourAlkynyloxy group, halogen
Optionally substituted by atoms (C₂-C_FourAlkenyl)
Even if it is substituted with an oxymethyl group or a halogen atom
Good (C₂-C_FourRepresents an alkynyl) oxymethyl group
Or, the formula:{In the formula, Z₃Represents a hydrogen atom or a halogen atom.
T₁And T₂Are the same or different and are hydrogen atom,
C which may be substituted with a rogen atom or a halogen atom₁
-C₃Substituted with an alkyl group, cyano group, or halogen atom
Optionally substituted with a phenyl group, halogen atom
May be (C₁-C_FourRepresents an alkoxy) carbonyl group
Or T₁And T₂And with (CH₂)_nIndicated by
Group (wherein n represents an integer of 2 to 5). }so
Represents the group shown or has the formula:(In the formula, B represents an oxygen atom or a sulfur atom)
Represents a group represented by or is represented by the formula:(In the formula, D represents a hydrogen atom or a halogen atom, and G
Is C optionally substituted with a halogen atom₁-C₆Al
Kill group, C₃-C_FiveCycloalkyl group or halogen source
Represents a phenyl group which may be substituted with a child. )〕so
Yes, or R₃Is the formula[In the formula, J is a halogen atom or substituted with a halogen atom.
May be C₁-C₆With an alkyl group or a halogen atom
C which may be substituted₁-C₆Represents an alkoxy group
You ] The ester compound according to claim 1. 3. A pest control agent comprising the ester compound according to claim 1 as an active ingredient. 4. A general formula: ## STR7 ## [In the formula, R ₁ represents a methyl group or a hydrogen atom, and R ₂
Represents a C ₁ -C ₆ haloalkyl group. ] The alcohol compound shown by these.