JP2001106665A - Geometrical isomer, its mixture and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylonitrile-based compound one of whose geometrical isomers is produced in a larger amount than the other and which is useful as an active ingredient for pest control agents. SOLUTION: The geometrical isomer of an acrylonitrile-based compound or its salt of formula (I) [T is phenyl or pyridyl substituted by R2; Q is phenyl, thienyl, pyridyl or benzyl which may be substituted by R3; R1 is C(=O)R4 or C(=S)R4] or its salt, or the mixture of the geometrical isomers, wherein the geometrical isomer has a longer retention time than that of the other geometrical isomer, when the mixture of the geometrical isomers is analyzed by reversed phase liquid chromatography which uses a polar solvent selected from water, methanol and acetonitrile as a mobile phase and further uses as a solid phase a filler comprising silica to which an alkyl group selected from trimethyl, octyl and octadecyl is chemically bound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a geometric isomer of an acrylonitrile compound useful as an active ingredient of a pesticide, a mixture thereof, and a method for producing the same.

[0002]

2. Description of the Related Art WO 98/35935 discloses an acrylonitrile compound or a salt thereof, and discloses that the compound has a geometric isomer. However, there is no disclosure of a specific method of producing one of the acrylonitrile-based compounds represented by the formula (I) or a salt thereof in one geometric isomer compound more than the other geometric isomer compound.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present inventors have conducted various studies on a method for producing one geometric isomer compound more than the other geometric isomer compound, and as a result, completed the present invention. That is, the present invention provides a compound represented by the formula (I):

[0004]

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[0005] wherein, T is pyridyl substituted with phenyl or R ₂ which is substituted with R _2, Q is optionally substituted with R ₃ may be substituted by phenyl, R ₃ thienyl,
Substituted with R ₃ is benzyl which may be substituted with may pyridyl or R _3, R ₁ is -C (= O) R ₄ or -C (=
S) R ₄ , wherein R ₂ and R ₃ are each halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkenyl Oxy, optionally substituted alkynyloxy, optionally substituted alkylthio, optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkenylthio, optionally substituted alkenylsulfinyl,
Optionally substituted alkenylsulfonyl, optionally substituted alkynylthio, optionally substituted alkynylsulfinyl, optionally substituted alkynylsulfonyl, nitro, cyano, optionally substituted phenyl, optionally substituted phenoxy, Optionally substituted phenylthio, optionally substituted phenylsulfinyl, optionally substituted phenylsulfonyl, optionally substituted benzyl, optionally substituted benzyloxy, optionally substituted benzylthio or optionally substituted Benzoyl and R ₄
Is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkenyloxy, optionally substituted alkynyloxy, optionally substituted alkylthio, optionally substituted alkenylthio, optionally substituted alkynylthio, cycloalkyl, cycloalkyloxy, _{cycloalkylthio, -N (R 5) R 6} , optionally substituted phenyl, optionally substituted phenoxy ,
Optionally substituted phenylthio, optionally substituted benzyl, optionally substituted benzyloxy be, optionally substituted benzylthio, -J, an -O-J or -S-J, R ₅ and R ₆ Each is hydrogen, alkyl or alkoxy, and J is a 5- or 6-membered heterocyclic group containing 1 to 4 at least one heteroatom selected from the group consisting of O, S and N (the heterocyclic group is substituted) (1) T is phenyl substituted with R ₂ , Q is thienyl optionally substituted with R ₃ , and R ₁ is —C (＝ O) ) R ₄ and R ₄ is optionally substituted alkyl, optionally substituted alkenyl,
Optionally substituted alkynyl, optionally substituted alkoxy, optionally alkenyloxy be substituted, an optionally substituted alkynyloxy, cycloalkyl, _{cycloalkyloxy, -N (R 5) R 6} , optionally substituted Good phenyl, optionally substituted phenoxy, optionally substituted phenylthio, optionally substituted benzyl, optionally substituted benzyloxy, optionally substituted benzylthio,
A compound which is -J, -OJ or -SJ, (2) T is phenyl substituted with R ₂ , Q is thienyl optionally substituted with R ₃ , and R ₁ is -C (= S) is R _4, and R ₄ is -N (R ₅₎ a R ₆ a compound, (3) T is pyridyl substituted with R _2, Q may be substituted by R ₃ Thienyl or pyridyl optionally substituted with R ₃ ,
A compound wherein R ₁ is —C (＝ O) R ₄ and R ₄ is alkyl; (4) α- (3,5-dimethoxyphenyl) —
β- (2-methoxy-4-methylphenyl) -β-acetoxyacrylonitrile and (5) α- (3,5-dimethoxyphenyl) -β- (2,6-dimethoxy-4-methylphenyl) -β-acetoxy (Acrylonitrile) is a geometric isomer of an acrylonitrile compound represented by the formula or a salt thereof or a mixture thereof, wherein a filler in which an alkyl group selected from trimethyl, octyl and octadecyl is chemically bonded to silica is used as a stationary phase, and water, methanol And when analyzed by reverse phase liquid chromatography using a polar solvent selected from acetonitrile as a mobile phase,
The present invention relates to a geometric isomer having a longer retention time, a geometric isomer mixture containing more of the geometric isomer, and a method for producing the same.

An optionally substituted alkyl for R ₂ or R ₃ ,
Alkenyl which may be substituted, alkynyl which may be substituted, alkoxy which may be substituted, alkenyloxy which may be substituted, alkynyloxy which may be substituted, alkylthio which may be substituted, alkyl which may be substituted Sulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkenylthio, optionally substituted alkenylsulfinyl, optionally substituted alkenylsulfonyl, optionally substituted alkynylthio,
Optionally substituted alkynylsulfinyl be and optionally substituted alkynylsulfonyl, and optionally substituted alkyl of R _4, alkenyl which may be substituted, alkynyl which may be substituted, an optionally substituted alkoxy, optionally substituted Alkenyloxy, optionally substituted alkynyloxy, optionally substituted alkylthio, optionally substituted alkenylthio and optionally substituted alkynylthio include, for example, halogen,
Alkoxy, haloalkoxy, alkoxycarbonyl,
Alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl,
Haloalkylsulfonyl, amino, monoalkylamino, dialkylamino, nitro, cyano.
The number of substitutions may be 1 or 2 or more, and in the case of 2 or more,
They may be the same or different.

Phenyl optionally substituted with R ₂ or R ₃ ,
Optionally substituted phenoxy, optionally substituted phenylthio, optionally substituted phenylsulfinyl, optionally substituted phenylsulfonyl, optionally substituted benzyl, optionally substituted benzyloxy, optionally substituted Benzylthio and optionally substituted benzoyl,
R ₄ optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylthio, optionally substituted benzyl, optionally substituted benzyloxy and optionally substituted benzylthio and heterocycle of J Examples of the substituent of the group include, for example, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, nitro, cyano, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, amino, monoalkylamino or dialkylamino Is mentioned. The number of substitutions may be one or more, and when two or more, they may be the same or different.

Examples of the heterocyclic group represented by J include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyrimidinyl, 1-pyrrolidinyl, 1-piperidinyl, 4-morpholino and the like. Is mentioned.

The alkyl or alkyl moiety contained in R ₂ , R ₃ , R ₄ , R ₅ or R ₆ has 1 to 6 carbon atoms and is linear or branched, for example, methyl, ethyl, propyl , Isopropyl, butyl, tert-butyl, pentyl,
Hexyl and the like. The alkenyl, alkynyl, alkenyl moiety or alkynyl moiety contained in R ₂ , R ₃ or R ₄ has 2 to 6 carbon atoms and is linear or branched, for example, vinyl, allyl, butadienyl, isopropenyl, Ethynyl, propynyl, 2-pentene-4-
Inyl and the like. Examples of the cycloalkyl or cycloalkyl moiety contained in R ₄ include those having 3 to 6 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl and the like.

The halogen contained in R ₂ , R ₃ , R ₄ or J or the halogen as a substituent includes each atom of fluorine, chlorine, bromine or iodine, and the number of substitution of the halogen as a substituent is 1 Or two or more, and in the case of two or more, they may be the same or different. The acrylonitrile compound of the formula (I) is capable of forming a salt, and includes any salt that is agriculturally acceptable, such as hydrochloride, sulfate, and nitrate. Inorganic acid salts; organic acid salts such as acetates and methanesulfonates; and the like.

In the present invention, the geometric isomer having a longer retention time refers to a geometric isomer mixture of the acrylonitrile compound represented by the formula (I) or a salt thereof (mixture of E-form and Z-form). When analyzed by reverse phase liquid chromatography (HPLC or the like) under the above conditions, the above formula (I)
Of the acrylonitrile compound or a salt thereof represented by the following formula (one is an E-form and the other is a Z-form), a compound corresponding to the latter peak. In addition, the geometric isomer mixture containing more geometric isomers having a longer retention time refers to a geometric isomer mixture in which the area of the peak after the peak is larger than the area of the previous peak among the two peaks. In addition, the geometric isomer mixture of the present invention preferably contains 60% or more, more preferably 80% or more, of the geometric isomer having a longer retention time.
The area ratio between the two peaks, ie, the preceding peak and the following peak, is preferably 40:60 or more, more preferably 20:80.
Refers to the above.

The geometric isomer having a longer retention time and the geometric isomer mixture containing more of the geometric isomer of the present invention can be produced according to the following reaction [A], [B] or [C]. it can.

[A]

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(Wherein T, Q and R ₁ are as described above, and X is a halogen) The compound represented by the formula (II) can be prepared by the method described in WO98 / 35935 or the method described below. It can be manufactured according to the method. Reaction [A] is usually performed in the presence of a base and a solvent. Examples of the base include alkali metals such as sodium and potassium; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; sodium hydride and potassium hydride Alkali metal hydrides such as trimethylamine, triethylamine, pyridine, 4-dimethylaminopyridine, 1,8-diazabicyclo [5.
One or more tertiary amines such as 4.0] -7-undecene are appropriately selected. Preferred bases are alkali metal carbonates, alkali metal hydrides or tertiary amines. More desirable bases are alkali metal carbonates or tertiary amines, especially sodium carbonate, potassium carbonate or 1,8-diazabicyclo [5.
4.0] -7-undecene is preferred. The amount of the base to be used is generally 1.0 to 2.5 equivalents, preferably 1.0 to 1.2 equivalents, relative to the compound of formula (II).

The solvent may be any solvent as long as it is inert to the reaction, for example, aliphatic hydrocarbons such as chloroform, dichloromethane, dichloroethane and trichloroethane; dioxane, tetrahydrofuran,
Ethers such as diethyl ether; esters such as methyl acetate and ethyl acetate; dimethyl sulfoxide;
Polar aprotic solvents such as sulfolane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile, propionitrile;
One or more of ketones such as acetone and methyl ethyl ketone are appropriately selected. Desirable solvents are aliphatic hydrocarbons, ethers, polar aprotic solvents or ketones. More desirable solvents are polar aprotic solvents or ketones, especially dimethylformamide, acetonitrile, acetone or methyl ethyl ketone. The reaction temperature of the reaction [A] is usually-
The reaction temperature is 80 to + 150 ° C, preferably -50 to + 120 ° C, more preferably 0 to 80 ° C.
The time is 1 to 48 hours, preferably 0.2 to 24 hours, more preferably 0.2 to 10 hours.

[B] A geometric isomer having a shorter retention time or a mixture of geometric isomers containing a larger amount of the geometric isomer having a shorter retention time when analyzed by reversed-phase liquid chromatography under the conditions described above. Isomerized under light irradiation. Incidentally, the geometric isomer having a short retention time or a mixture thereof can be produced according to the method described in WO98 / 35935. Reaction [B] is characterized by isomerizing the above-mentioned geometric isomer having a shorter retention time into a geometric isomer having a longer retention time under light irradiation. The expression is as follows.

[0017]

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Wherein Q is as described above, one of A and B is T and the other is R ₁ (T and R ₁ are as described above), and β has a shorter retention time (Indicating geometric isomers, α indicating geometric isomer with longer retention time) Reaction [B] is carried out under light irradiation, more specifically under UV irradiation. The light source is not limited, for example, sunlight, mercury lamp, laser, deuterium lamp,
A metal halide lamp and the like are mentioned, and among them, a sunlight or a mercury lamp is desirable.

Reaction [B] is carried out in the presence of a solvent, if desired. The solvent may be any solvent as long as it is inert to the reaction, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbons such as hexane and cyclohexane; dioxane; Ethers such as tetrahydrofuran and diethyl ether; esters such as methyl acetate and ethyl acetate; polar non-protons such as dimethyl sulfoxide, sulfolane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, pyridine, acetonitrile and propionitrile Ketones such as acetone and methyl ethyl ketone; amines such as monomethylamine, dimethylamine and triethylamine; acetic acid;
One or more kinds are appropriately selected from organic acids such as propionic acid. Desirable solvents are non-polar solvents, for example, aromatic or aliphatic hydrocarbons. More desirable solvents are benzene, toluene or hexane.

Since the reaction [B], that is, the above-mentioned isomerization is not affected by the temperature, the reaction temperature may be any temperature. Therefore, usually around room temperature, specifically, 0 to 30 ° C
You can do it at The reaction time in the reaction [B] is such that the concentration of the geometric isomer having a shorter retention time or the geometric isomer mixture containing more of the geometric isomer having the shorter retention time is, for example, 10 ⁻³ to 1 mol / l. If there is, isomerization can be usually performed in 0.5 to 24 hours, desirably in about 1 to 8 hours. The reaction [B] is desirably performed in the presence of an inert gas, and examples of the inert gas include nitrogen, helium, and argon.

[C]

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(Wherein T, Q, R ₁ and X are as described above, and Z is halogen or alkoxy). Steps (1) and (2) of reaction [C] are carried out in the same reactor. Can be performed continuously. Reaction [C] is usually performed in the presence of a base and a solvent. Examples of the base include an alkali metal such as sodium and potassium; an alkali metal hydride such as sodium hydride and potassium hydride; trimethylamine, triethylamine, pyridine, 4-dimethylaminopyridine, 1,8-diazabicyclo [5.
Tertiary amines such as 4.0] -7-undecene; one or more kinds are appropriately selected from organic lithiums such as methyllithium, n-butyllithium, tert-butyllithium, and phenyllithium. . Desirable bases are
It is a strong base, more specifically an alkali metal hydride or organolithium. More desirable bases are alkali metal hydrides, especially sodium hydride or potassium hydride. The amount of the base to be used is generally 2.0-2.5 equivalents, desirably 2.0 equivalents, relative to compound of formula (IV).
1 to 2.2 equivalents. The base may be appropriately added at the time of performing the step (2), which may accelerate the reaction.

The solvent may be any solvent as long as it is inert to the reaction, for example, benzene, toluene,
Aromatic hydrocarbons such as xylene; ethers such as dioxane, tetrahydrofuran and diethyl ether; esters such as methyl acetate and ethyl acetate; dimethyl sulfoxide, sulfolane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, pyridine , Acetonitrile, propionitrile, and other polar aprotic solvents; and one or more of ketones such as acetone and methyl ethyl ketone. Desirable solvents are aromatic hydrocarbons, ethers or dimethylacetamide in polar aprotic solvents,
It is dimethylformamide. More desirable solvents are dimethylacetamide and dimethylformamide in ethers or polar aprotic solvents, among which tetrahydrofuran or dimethylformamide is preferred. The solvent may be appropriately added when performing the step (2).

The reaction [C] is carried out via the intermediate compound produced in the step (1). The intermediate compound varies depending on the type of the base used, and when an alkali metal-containing base or a tertiary amine is used, a compound represented by the formula:

[0025]

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(Where T and Q are as described above, and M
Is an alkali metal or a tertiary amine conjugate acid), and when another base is used,
formula;

[0027]

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(Wherein T and Q are as defined above). The reaction temperature of the reaction [C] is
Usually -80 to + 150 ° C, preferably -50 to +120
° C, more preferably 0 to 80 ° C, and the reaction time is usually 0.1 to 48 hours, preferably 0.5 to 24 hours, more preferably 1 to 6 hours.

The mixture of geometric isomers produced in the above reaction [A], [B] or [C] can be purified to increase the ratio of the geometric isomer having the longer retention time. A purification method includes recrystallization performed in the presence of a solvent. The recrystallization is performed under heating if desired. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and chlorobenzene; aliphatic hydrocarbons such as hexane, isoparaffin and cyclohexane; ethers such as dioxane, tetrahydrofuran and diethyl ether; methyl acetate and ethyl acetate Alcohols such as methanol, ethanol, and isopropanol; polar aprotic solvents such as acetonitrile and propionitrile; and one or more of ketones such as acetone and methyl ethyl ketone. Selected. Desirable solvents are aliphatic hydrocarbons or alcohols.

An example of a method for producing the compound represented by the formula (II) will be described. [D]

[0031]

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(Wherein T, Q and Z are as described above) The reaction [D] is usually carried out in the presence of a base and a solvent. Examples of the base include alkali metals such as sodium and potassium; alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium tertiary butyrate; alkali metal hydrides such as sodium hydride and potassium hydride ; Methyllithium, n-
One or more kinds are appropriately selected from organic lithiums such as butyllithium, tert-butyllithium, and phenyllithium. Preferred bases are alkali metal alcoholates or alkali metal hydrides, of which potassium tertiary butyrate, sodium hydride or potassium hydride is preferred. The amount of the base to be used is generally 2.0-2.5 equivalents, preferably 2.0-2.5 equivalents, relative to compound of formula (IV).
2.2 equivalents.

The solvent may be any solvent as long as it is inert to the reaction, for example, benzene, toluene,
Aromatic hydrocarbons such as xylene and chlorobenzene;
Ethers such as dioxane, tetrahydrofuran and diethyl ether; alcohols such as methanol, ethanol, propanol and tert-butanol; and one or more kinds are appropriately selected from polar aprotic solvents such as dimethylformamide and the like. . However, when Z is a halogen, the use of alcohols is not preferred. Preferred solvents are aromatic hydrocarbons, ethers or polar aprotic solvents. More desirable solvents are ethers or polar aprotic solvents, especially tetrahydrofuran or dimethylformamide. The reaction temperature of the reaction [D] is usually -80 to + 150 ° C, preferably -50 to + 120 ° C, more preferably 0 to 120 ° C.
The reaction time is generally 0.1 to 48 hours, preferably 0.5 to 24 hours, more preferably 0.5 to 10 hours.

The geometric isomer having a longer retention time and the geometric isomer mixture containing more of the geometric isomer (hereinafter collectively abbreviated as the compound of the present invention) of the present invention can provide a more effective pest control agent. Useful as an ingredient. In particular, it is useful as an active ingredient of a pesticide such as an insecticide, acaricide, a nematicide, a soil pesticide, a bactericide, and a pesticide in water. Desirable embodiments of the pesticidal composition containing the compound of the present invention are described below. First, pest control agents such as insecticides, acaricides, nematicides, soil pesticides, and fungicides are described.

The pesticidal composition containing the compound of the present invention is useful as an insecticide, acaricide, nematocide, or a soil pesticide (hereinafter abbreviated as a pesticide).
Plant parasitic mites such as red mite, Kanzawa spider mite, mandarin red mite, apple spider mite, red mite, red mite, red mite, etc .; animal parasitic mites such as ticks; aphids such as peach aphid, cotton aphid; , Beetle, cutworm, codling moth, ball worm, tobacco bad worm, gypsy moth, cob beetle, chanokokakumon hamaki, colorado potato beetle, beetle beetle, ballweedville, planthopper, leafhopper, beetle, stinkbug, whitefly, thrips Agricultural pests such as grasshoppers, flies, scarab beetles, tamayanaga, kaburayaga, ants, etc .; Plant-parasitic nematodes such as Chuu, pine wood nematode, etc .; Sanitary pests such as;
Stored pests such as adzuki beetles, skull beetles, beetles, etc .;
It is effective for controlling clothing such as termites, house pests; indoor dust mites such as Dermatophagoides farinae, Dermatophagoides farinae, and red ticks; other fleas, lice and flies parasitic on livestock. Above all, pesticides containing the compound of the present invention are particularly useful for controlling plant parasitic mites, animal parasitic mites, agricultural pests, sanitary pests, clothing, house pests, indoor dust mites, and the like. It is valid. Further, a pesticide containing the compound of the present invention, an organic phosphorus agent,
It is also effective in controlling various pests that are resistant to drugs such as carbamates and synthetic pyrethroids. Further, since the compound of the present invention has excellent systemic migration properties, by treating the soil with a pesticide containing the compound of the present invention, soil harmful insects, mites, nematodes, gastropods In addition, pests in the foliage can be controlled simultaneously with the control of isopods.

The pesticidal composition containing the compound of the present invention is useful as a fungicide. For example, rice blast, sheath blight, sesame leaf blight; powdery mildew of wheat and red mold Rust, snow rot, naked smut, eye spot, leaf blight, blight; citrus black spot, scab; apple monilia, powdery mildew, spot leaf spot, scab; pear Scab of the
Black spot; peach scab, scab, phomopsis rot;
Grape scab, late rot, powdery mildew, downy mildew; oyster anthracnose, deciduous disease; cucurbits anthracnose, powdery mildew, vine wilt, downy mildew; tomato ring print It is effective for controlling diseases such as disease, leaf mold, plague; black spot on cruciferous vegetables; summer plague, plague on potato; powdery mildew on strawberry; gray mold, sclerotium on various crops. It is also effective in controlling soil diseases caused by plant pathogens such as Fusarium, Picium, Rhizoctonia, Verticillium, and Plasmodiophora. Another desirable embodiment of the pesticide containing the compound of the present invention,
Pest control agents for agricultural and horticultural use that comprehensively control the above-mentioned plant parasitic mites, agricultural pests, plant parasitic nematodes, gastropods, soil pests, various diseases, various soil diseases, and the like.

The pesticides such as pesticides and fungicides containing the compound of the present invention are usually mixed with the compound and various agricultural auxiliaries to prepare powders, granules, water dispersible granules, Formulations, aqueous suspensions, oil suspensions, aqueous solvents, emulsions, pastes, aerosols, microsprays, etc., and are usually used as long as they meet the purpose of the present invention. In any form used in the art. Auxiliaries used in the formulation include diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, a mixture of kaolinite and sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate,
Solid carriers such as zeolite and starch; water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, alcohol, etc. Solvents; fatty acid salts, benzoates, alkylsulfosuccinates, dialkylsulfosuccinates, polycarboxylates, alkyl sulfates,
Alkyl sulfate, alkyl aryl sulfate, alkyl diglycol ether sulfate, alcohol sulfate, alkyl sulfonate, alkyl aryl sulfonate, aryl sulfonate, lignin sulfonate,
Alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate ester salt, alkyl aryl phosphate, styryl aryl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene Alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate,
Anionic surfactants and spreading agents such as salts of naphthalenesulfonic acid formalin condensate; sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid polyglyceride, fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, oxyalkylene block Polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, poly Nonionic surfactants such as oxyethylene hydrogenated castor oil and polyoxypropylene fatty acid esters Vegetable oils such as olive oil, kapok oil, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, cutting oil, liquid paraffin, etc. Is mentioned. These adjuvants can be selected from those known in the art without departing from the purpose of the present invention. In addition, various commonly used auxiliary agents such as a bulking agent, a thickener, an antisettling agent, an antifreezing agent, a dispersion stabilizer, a safener, and a fungicide can also be used.
The compounding ratio of the compound of the present invention and various auxiliaries is 0.001:
99.999-95: 5, desirably 0.005: 9
9.999 to 90:10. In actual use of these preparations, they can be used as they are, or can be used after being diluted to a predetermined concentration with a diluent such as water and adding various spreading agents as necessary.

The application of a pesticide such as a pesticide or fungicide containing the compound of the present invention is generally defined by differences in weather conditions, formulation form, application time, place of application, types and occurrence of pests and the like. No, but generally 0.05-
800,000 ppm, preferably 0.5 to 500,000
The concentration of the active ingredient is set to ppm, and the application rate per unit area is 0.05 to 0.005 to 1 / ha of the compound of the present invention.
It is 10,000 g, desirably 1 to 5000 g. The application of the pesticide, which is a desirable embodiment of the pesticidal composition containing the compound of the present invention, cannot be specified unconditionally due to the difference in various conditions as described above, but is generally 0.1 to 500,000.
ppm, preferably 1 to 100,000 ppm of the active ingredient concentration, the application rate per unit area is 0.1 to 10000 g, preferably 10 to 1000 g, of the compound of the present invention per hectare. As described above, it cannot be specified unconditionally due to differences in various conditions, but is generally 0.1 to 500,000 ppm, preferably 1 to 10 ppm.
The active ingredient concentration is 0000 ppm, and the application rate per unit area is 0.1 to 10000 g, preferably 10 to 1000 g, of the compound of the present invention per hectare. Further, the application of the pesticidal composition for agricultural and horticultural use, which is another desirable embodiment of the pesticidal composition containing the compound of the present invention, is performed in accordance with the application of the pesticide and the fungicide. The present invention also includes a method for controlling harmful pests by such an application method.

The application of various formulations of a pesticide such as a pesticide or fungicide containing the compound of the present invention, or a dilution thereof is carried out by a generally applied application method, that is, spraying (eg, spraying, spraying) Misting, atomizing, granulation, water surface application, etc.), soil application (mixing, irrigation, etc.), surface application (coating, dressing, coating, etc.), immersion poison bait and the like. Further, it is also possible to feed the livestock with the above-mentioned active ingredient mixed with the feed to control the development and growth of harmful insects, particularly harmful insects, in the excrement. Also, a so-called ultra-high concentration small amount spraying method (ultra low v)
olume). In this method, it is possible to contain 100% of the active ingredient.

Further, a pesticide containing the compound of the present invention,
Pest control agents such as fungicides can be mixed or used in combination with other agricultural chemicals, fertilizers, safeners, and the like, and in this case, more excellent effects and effects may be exhibited. Other pesticides include herbicides, pesticides, acaricides, nematicides, soil pesticides, fungicides, antivirals, attractants, antibiotics,
Plant hormones, plant growth regulators and the like. In particular, a mixed pest control composition in which the compound of the present invention and one or more kinds of active ingredient compounds of other pesticides are mixed or used in combination, the application range, the timing of chemical treatment, the control activity, etc. in a favorable direction. It is possible to improve. The compound of the present invention and the active ingredient compound of another pesticide may be separately prepared and used by mixing at the time of spraying, or both may be prepared and used together. The present invention also includes such a mixed pest control composition. The mixing ratio between the compound of the present invention and the active ingredient compound of another pesticide cannot be specified unconditionally due to differences in weather conditions, preparation form, application time, place of application, types and occurrence of pests, but generally from 1: 300 to 300:
1, preferably 1: 100 to 100: 1. Also,
The suitable application amount is 0.1 to 5000 g, preferably 10 to 3000 g, as the total amount of the active ingredient compound per hectare. The present invention also includes a method for controlling pests and pests by a method for applying such a mixed pest control composition.

Examples of the pesticides, acaricides, nematicides or soil pesticides in the above-mentioned other pesticides, that is, the active ingredient compounds of the pesticides (generic names; including some applications) include, for example, Profenofos, Dichlorvos, Fenamiphos (Fe
namiphos), fenitrothion (Fenitr)
othion), EPN, diazinon (Diazin)
on), chlorpyrifif (Chlorpyrif)
os-methyl), acephate (Acephat)
e), Prothiofos, Fosthiazate, Phosphocarb, Cadusafos
afos), organophosphate compounds such as Disulfoton;

Carbaryl, Propoxur, Aldicarb
carb), Carbofuran,
Thiodicarb, Methomil (M
ethomyl), oxamyl (Oxamyl), ethiophencarb (Ethiofencarb), pirimicarb (Pirimicarb), fenobucarb (F
enobucarb), Carbosulfan (Carbo)
sulfan), Benfuracab
carbamate compounds such as rb);

Nereistoxin derivatives such as Cartap and Thiocyclam; organic chlorinated compounds such as Dicofol and Tetradifon;
Fenbutatin Oxid
e) organometallic compounds such as fenvalerate (F
evalerate), permethrin (Permet)
hrin), cypermethrin (Cypermethri)
n), Deltamethrin,
Pyrethroid compounds such as Cyhalothrin, Tefluthrin, Ethofenprox;

Diflubenzuron (Diflubenzu)
ron), chlorfluazuron (Chlorfluaz)
uron), teflubenzuron
ron), Flufenoxur
on), immature hormone-like compounds such as methoprene; pyridazinone-based compounds such as pyridaben; fenpyroximate
oximate), fipronil (Fiproni)
l), Tebufenpyrad (Tebufenpyra)
d), pyrazole-based compounds such as ethiprole, tolfenpyrad;

Imidacloprid (Imidcloprr)
id), Nitenpyram, Acetamiprid, Thiacloprid, Thiamethoxam (Th)
iamethoxam), clothianidin (Cloth)
ianidin), dinotefuran (Dinotefur)
an), etc .; tebufenozide (Te
bufenozide), methoxyphenozide (Met)
hoxyfenozide), chromafenozide (Ch)
hydrazine-based compounds such as romafenozide);

Dinitro compounds, organic sulfur compounds, urea compounds, triazine compounds, hydrazone compounds, and other compounds such as buprofezin (Bupr
ofezin), Hexythiazox (Hexithia)
zox), Amitraz, Chlordimform, Silafluofen, Triazamate (T
riazamate), pymetrozine (Pymetro)
zine), pyrimidifen
n), Chlorfenapyr (Chlorfenapy)
r), Indoxacarb, Acequinocyl, Etoxazole, Cyromazine (Cyroma)
zine), 1,3-dichloropropene (1,3-di)
chloropropene); and the like. Furthermore, microbial pesticides such as BT agents, entomopathogenic virus agents, etc., avermectin (Avermectin)
in), antibiotics such as milbemycin, spinosad and the like can be mixed and used in combination.

Examples of the active ingredient compound of the fungicide (generic name; partially included) in the other pesticides include, for example, mepanipyrim, pyrimethanil, and cyprodinil.
pyrimidinamine-based compounds such as Rodilin);

[0048] Triadimefon (Triadimefo)
n), Bitertanol, Triflumizole, Etaconazole, Propiconazole, Penconazole (P)
Enconazole, Flusilazole (Flusi)
lazole), microbutanil (Myclobut)
anil), cyproconazole (Cyproconaz)
ole), terbuconazole (Terbuconazo)
le), Hexaconazole
e), Furconazole
-Cis), Prochloraz,
Azole compounds such as metconazole, epoxyconazole, epoxyconazole, tetraconazole, oxpoconazole, sipconazole;

Quinomethionate (Quinomethi)
quinoxaline-based compounds such as maneb (Maneb), zineb (Zineb), manzeb (M
ancozeb), polycarbamate (Polycar)
dithiocarbamate-based compounds such as bamate) and propineb (Propineb);
alide), chlorothalonil (Chlorothal)
onil), organochlorine-based compounds such as Quintozene; Benomyl,
Thiophanate methyl (Thiophanate-Me)
thyl), Carbendazi (Carbendazi)
m), an imidazole-based compound such as 4-chloro-2-cyano-1-dimethylsulfamoyl-5- (4-methylphenyl) imidazole;

Pyridinamine compounds such as Fluazinam; Simoxanil (Cymox)
anil), such as cyanoacetamide-based compounds; metalaxyl, oxadixyl (O
xadixyl), off-race (Ofrace), benalaxyl, fralaxyl (F
uraaxyl), cyprofuram (Cyprofur)
am); sulfenic compounds such as Dichlofluanid; cupric hydroxide;
xide), copper-based compounds such as organic copper (Oxine Copper);

Hydroxoxazole (Hydrox)
isoxazole-based compounds such as yisoxazole; fosetyl aluminum (Fosetyl-Al);
Turkish phos-methyl (Tolcofos-Methy
l), organophosphorus compounds such as S-benzyl O, O-diisopropyl phosphorothioate, O-ethyl S, S-diphenyl phosphorodithioate, aluminum ethyl hydrogen phosphonate; captan (Cap
N-halogenothioalkyl-based compounds such as tan), Captafol, and Folpet; Procymidon
e), dicarboximide compounds such as Iprodione, Vinclozolin;

Flutolanil,
Mepronil, Zoxamide (Zox)
Amide); Piperazine compounds such as Triforine; Pyridine compounds such as Pyrifenox; Fenarimo
l), carbinol-based compounds such as Flutriafol; fenpropidin (Fe
piperidine compounds such as npropidine);

Fenpropimorph
morphine-based compounds such as fentin hydroxide (Fentin Hydroxide),
Fentin Acetat
e) organotin compounds such as e); peniculone (Pe)
urea-based compounds such as Ncycuron; cinamic acid-based compounds such as Dimethomorph; Diethofencarb
phenylcarbamate-based compounds such as carb);

Fludioxonil
l), cyanopyrrole-based compounds such as fenpiclonil; Azoxystrobin, Kresoxim-methyl, Metominofen, Trifloxystrobin, picoxybin A strobilurin-based compound such as Famoxadone;
oxazolidinone compounds such as e); thiazole carboxamide compounds such as ethaboxam;

Silthiopham (Silthiopham)
m); aminoacid amide carbamates such as Iprovalicarb; phenamidone (Fena)
Midone); hydroxyanilide compounds such as Fenhexamide; Flusulfamide (Plus)
benzene sulfonamide-based compounds such as ulfamide);

Atraquinone compounds; crotonic acid compounds; antibiotics and other compounds such as isoprothiolane, tricyclazole, and pyroquilone
roquilon), diclomedine (Dicromez)
ine), probenazole (Pro.benazol)
e), quinoxyfen, propamocarb hydrochloride (Propamocarb Hydr)
ochloride), spiroxamine (Spirox)
amine), Chlorpicrin (Chloropicr)
in), dazomet, Carbam sodium salt (Metam-sodium); and the like.

Next, a pest control agent such as a water-adhering biocontrol agent will be described. The underwater biocontrol agent containing the compound of the present invention can be used for ships, underwater structures (for example, port facilities, buoys, pipelines, bridges, submarine bases, offshore oilfield drilling facilities, headrace pipes of power plants, stationary nets, culture nets) Control of harmful organisms attached to harmful water, such as plants such as green algae and brown algae, animals such as barnacles, serpula, sea squirts, mussels and oysters, various bacteria called slime, and molds It is effective in preventing aquatic organisms such as diatoms from adhering to the bottom of ships and underwater structures and preventing their propagation.

The agent for controlling underwater organisms containing the compound of the present invention imparts antifouling properties and slime resistance over a long period of time, and exhibits an excellent effect of preventing harmful underwater organisms from adhering to and reproducing on ships and underwater structures. . The water-borne biocontrol agent containing the compound of the present invention is usually formulated and used as a coating composition, but may be formulated and used in other dosage forms (solutions, emulsions, pellets, etc.) in some cases. . Examples of the paint vehicle used when formulating the compound of the present invention as a paint composition include resin vehicles that are usually used. For example, vinyl chloride resins and vinyl chloride-
Vinyl acetate copolymer, vinyl chloride-vinyl isobutyl ether copolymer, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic resin, styrene-butadiene resin, polyester resin, epoxy resin, phenol resin Resin, synthetic rubber, silicone rubber, silicone resin, petroleum resin, oil and fat resin, rosin ester resin, rosin soap, rosin and the like. Further, as a vehicle having antifouling properties, an organic tin compound salt of an unsaturated mono- or dicarboxylic acid obtained by a condensation reaction of (meth) acrylic acid with an organic tin compound such as bis (tributyltin) oxide or triphenyltin hydroxide. An acrylic copolymer resin composition containing as a constituent unit, a resin containing a metal element such as copper, zinc, tellurium in a side chain, or the like can also be used.

When the compound of the present invention is formulated as a coating composition, the compounding ratio is 0.1 to 60 with respect to the whole coating composition.
The preparation is prepared so as to contain the compound of the present invention by weight, preferably 1 to 40% by weight. The coating composition containing the compound of the present invention can be prepared, for example, using a ball mill, a pebble mill, a roll mill, a sand glider mill, or the like according to a method well known in the field of paint production. Further, the coating composition can contain a plasticizer, a coloring pigment, an extender, an organic solvent, and the like, which are generally used in the art.

The coating composition containing the compound of the present invention may further contain other known inorganic or organic antifouling agents, if necessary. Examples of such antifouling agents include, for example, cuprous oxide, copper rhodanide, copper hydroxide, copper naphthenate, metallic copper, various tin compounds and dithiocarbamic acid derivatives, for example, tetramethylthiuram monosulfide, tetramethylthiuram disulfide Zinc bis- (dimethyldithiocarbamate), zinc ethylene-bis (dithiocarbamate), manganese ethylene-bis (dithiocarbamate), bis- (dimethyldithiocarbamate)
Copper.

The preferred embodiments of the present invention are as follows. [1] A geometric isomer of the acrylonitrile compound represented by the formula (I) or a salt thereof, which has a longer retention time when analyzed by reversed-phase liquid chromatography under the above-mentioned conditions. A geometric isomer, wherein the isomer is an E-isomer. [2] A geometric isomer of the acrylonitrile compound represented by the formula (I) or a salt thereof, which has a longer retention time when analyzed by reversed-phase liquid chromatography under the above-mentioned conditions. A geometric isomer, wherein the isomer is a Z-isomer.

[3] Among the geometric isomers of the acrylonitrile compound represented by the formula (I) or a salt thereof or a mixture thereof, a longer retention time when analyzed by reversed-phase liquid chromatography under the conditions described above. A geometric isomer mixture comprising at least 80% of geometric isomers having time. [4] Among the geometric isomers of the acrylonitrile compound represented by the formula (I) or a salt thereof or a mixture thereof, the acrylonitrile compound has a longer retention time when analyzed by reversed-phase liquid chromatography under the conditions described above. A geometric isomer mixture comprising at least 90% of a geometric isomer.

[5] Among the geometric isomers of the acrylonitrile compound represented by the formula (I) or a salt thereof or a mixture thereof, a longer retention time when analyzed by reversed-phase liquid chromatography under the conditions described above. A geometric isomer mixture comprising 95% or more of a geometric isomer having time. [6] A geometric isomer produced by the method of the reaction [A] or a mixture of geometric isomers containing a larger amount of the geometric isomer. [7] A geometric isomer produced by the method of the reaction [B] or a mixture of geometric isomers containing a larger amount of the geometric isomer. [8] A geometric isomer produced by the method of the above reaction [C] or a mixture of geometric isomers containing more of the geometric isomer.

[9] A method in which in the above reaction [A], an alkali metal carbonate or a tertiary amine is used as a base, and a polar aprotic solvent or a ketone is used as a solvent. [10] In the reaction [A], sodium carbonate, potassium carbonate or 1,8-diazabicyclo [5.
4.0] -7-undecene, and using dimethylformamide, acetonitrile, acetone or methyl ethyl ketone as a solvent. [11] A method in which in the reaction [A], an alkali metal carbonate is used as a base, and a polar aprotic solvent or a ketone is used as a solvent. [12] A method in the above reaction [A], wherein sodium carbonate or potassium carbonate is used as a base, and dimethylformamide, acetonitrile, acetone or methyl ethyl ketone is used as a solvent. [13] A geometric isomer produced by the method of the above [9], [10], [11] or [12] or a mixture of geometric isomers containing more of the geometric isomer.

[14] A method of using a non-polar solvent as a solvent in the above reaction [B] under irradiation with ultraviolet rays. [15] A method in which in the reaction [B], an aromatic hydrocarbon or an aliphatic hydrocarbon is used as a solvent under ultraviolet irradiation. [16] A method using benzene, toluene or hexane as a solvent in the reaction [B] under irradiation with ultraviolet light. [17] In the above reaction [B], a method using sunlight or a mercury lamp as a light source and using benzene, toluene or hexane as a solvent. [18] A geometric isomer produced by the method of the above [14], [15], [16] or [17] or a mixture of geometric isomers containing more of the geometric isomer.

[19] In the above reaction [C], a method in which a strong base is used as a base and aromatic hydrocarbons, ethers or a polar aprotic solvent is used as a solvent. [20] A method in which in the reaction [C], an alkali metal hydride or organolithium is used as a base, and dimethylacetamide or dimethylformamide in a polar aprotic solvent is used as a solvent. [21] In the reaction [C], sodium hydride, potassium hydride, methyl lithium, n-butyl lithium, tert-butyl lithium or phenyl lithium is used as a base, and dioxane, tetrahydrofuran, diethyl ether, dimethylacetamide or A method using dimethylformamide. [22] A method in which in the above reaction [C], an alkali metal hydride is used as a base, and dimethylacetamide or dimethylformamide in a polar aprotic solvent is used as a solvent. [23] A method in which in the reaction [C], sodium hydride or potassium hydride is used as a base, and tetrahydrofuran or dimethylformamide is used as a solvent. [24] A geometric isomer produced by the method according to the above [19], [20], [21], [22] or [23] or a mixture of geometric isomers containing more of the geometric isomer.

[25] A compound or a salt thereof, wherein the geometrical isomer of the acrylonitrile compound represented by the above formula (I) is E-form. [26] A compound or a salt thereof, wherein the geometric isomer of the acrylonitrile-based compound represented by the formula (I) is a Z-isomer. [27] The above-mentioned [1] to [26] when R ₁ in the above formula (I) is —C (＝ O) R ₄ . [28] The above-mentioned [1] to [26] when R ₁ in the above formula (I) is —C (＝ S) R ₄ . [29] A pest control agent comprising, as an active ingredient, the geometric isomer of the above [1] to [28] or a geometric isomer mixture containing the geometric isomer in a larger amount. [30] An insecticide, miticide or nematicide containing the geometric isomer of the above [1] to [28] or a mixture of geometric isomers containing the geometric isomer in a larger amount as an active ingredient. [31] A method for controlling pests, which comprises using the geometric isomers of the above [1] to [28] or a mixture of geometric isomers containing more of the geometric isomers as an active ingredient on pests.

[0068]

EXAMPLES Next, examples of the present invention will be described, but the present invention is not limited to these examples. The isomer ratio in each synthesis example refers to the ratio of a geometric isomer having a shorter retention time to a geometric isomer having a longer retention time [HPLC
(Reverse phase liquid chromatography) Peak area ratio in ultraviolet absorption detector].

Synthesis Example 1 Synthesis of α- (4-tert-butylphenyl) -β-[(ethylthio) carbonyloxy] -β- (2-trifluoromethylphenyl) acrylonitrile (isomer ratio 2:98, compound A) Synthesis 68% sodium hydride 0.83 g and dimethylformamide 13
To a mixture of ml, 2.0 g of 4-tert-butylbenzyl cyanide,
A mixture of 2.34 g of 2-trifluoromethylbenzoyl chloride and 8 ml of dimethylformamide was added dropwise while maintaining the temperature at 40 ° C. After the completion of the addition, the mixture was reacted at room temperature for 30 minutes. The reaction mixture was ice-cooled and ethyl chloroformate 1.77 g
And 1.2 ml of dimethylformamide was added dropwise, and after completion of the addition, the mixture was reacted under ice cooling for 30 minutes. The reaction mixture was poured into cold water, extracted with methylene chloride, washed with water, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/9) to obtain 3.9 g of the desired product (isomer ratio 2:98) having a melting point of 116 to 117 ° C. Analyzed this one
The HPLC conditions and the NMR spectrum data of this are as follows. HPLC conditions Stationary phase: Octadecyl-based column (trade name: wakosil-II5)
C18), 4.6 mm × 250 mm; Wako Pure Chemical Industries mobile phase: acetonitrile / water = 4/1 (V / V) Detection wavelength: 254 nm Column temperature: 40 ° C. Flow rate: 1 ml / min ¹ H-NMR δppm (Solvent: (CDCl ₃ / 400MHz) 1.17 (t, 3H), 1.31 (s, 9H), 2.75 (q, 2H), 7.46 (d, 2H), 7.58
(d, 2H), 7.61 (t, 1H), 7.68 (t, 1H), 7.77 (d, 1H), 7.83 (d, 1H)

Synthesis Example 2 α- (4-tert-butylphenyl) -β-[(n-propyloxy)
Synthesis of carbonyloxy] -β- (2-trifluoromethylphenyl) acrylonitrile (isomeric ratio 7:93, compound B) 0.84 g of 68% sodium hydride and dimethylformamide 13
To a mixture of ml, 2.0 g of 4-tert-butylbenzyl cyanide,
A mixture of 2.35 g of 2-trifluoromethylbenzoyl chloride and 8 ml of dimethylformamide was added dropwise while maintaining the temperature at 40 to 50 ° C. After the completion of the addition, the mixture was reacted at room temperature for 30 minutes. The reaction mixture was ice-cooled, and a mixture of 1.5 g of n-propyl chloroformate and 1.2 ml of dimethylformamide was added dropwise. After the completion of the addition, the mixture was reacted for 30 minutes under ice-cooling. The reaction mixture was poured into cold water, extracted with methylene chloride, washed with water, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/9), and the target compound having a melting point of 44 to 45 ° C
(Isomer ratio 7:93) 3.4 g was obtained. The HPLC conditions for analyzing this product were the same as those in Synthesis Example 1 described above. In addition, N
The MR spectrum data is as follows. ¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz) 0.84 (t, 3H), 1.33 (s, 9H), 1.57 (m, 2H), 4.01 (t, 2H), 7.45
(d, 2H), 7.61 (d, 2H), 7.64 (t, 1H), 7.68 (t, 1H), 7.77 (d, 1
H), 7.86 (d, 1H)

Synthesis Example 3 α- (4-tert-butylphenyl) -β- [ethoxy (thiocarbonyl) oxy] -β- (2-trifluoromethylphenyl) acrylonitrile (isomer ratio 35:65, compound C) Synthesis of 68% sodium hydride 0.83 g and dimethylformamide 13
To a mixture of ml, 2.0 g of 4-tert-butylbenzyl cyanide,
A mixture of 2.34 g of 2-trifluoromethylbenzoyl chloride and 8 ml of dimethylformamide was added dropwise while maintaining the temperature at 40 to 50 ° C. After the completion of the addition, the mixture was reacted at room temperature for 30 minutes. The reaction mixture was ice-cooled, and a mixture of 2.1 g of ethyl chlorothioformate and 1.2 ml of dimethylformamide was added dropwise. After completion of the addition, the mixture was reacted for 30 minutes under ice-cooling. The reaction mixture was poured into cold water, extracted with methylene chloride, washed with water, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/9) to give the desired product with a melting point of 62-64 ° C.
(Isomer ratio: 35:65) 3.2 g was obtained. HPLC that analyzed this
Are the same as in Synthesis Example 1. The NMR spectrum data of each geometric isomer is as follows. ¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz) Geometric isomer with shorter retention time: 1.23 (s, 9H), 1.4
0 (t, 3H), 4.49 (q, 2H), 7.07 (d, 2H), 7.22 (d, 2H), 7.37 (d, 1
H), 7.47 (t, 1H), 7.57 (t, 1H), 7.73 (d, 1H) Geometric isomer with retention time longer than: 1.27 (t, 3H), 1.3
5 (s, 9H), 4.39 (q, 2H), 7.44 (d, 2H), 7.58 (d, 2H), 7.60 (t, 1
H), 7.66 (t, 1H), 7.76 (d, 1H), 8.02 (d, 1H)

Synthesis Example 4 Synthesis of α- (4-tert-butylphenyl) -β-[(methylthio) carbonyloxy] -β- (2-trifluoromethylphenyl) acrylonitrile (14:86 isomer ratio, compound D) Synthesis α- (4-tert-butylphenyl) -β-hydroxy-β- (2-trifluoromethylphenyl) acrylonitrile 3.0 g and trichloroethane 1.14 g in a mixture of 25 ml of dichloroethane
Was added thereto, and a mixture of 1.19 g of methyl chlorothiol formate and 5 ml of dichloroethane was added dropwise thereto under ice cooling.
After the completion of the dropwise addition, the mixture was reacted for 15 minutes under ice cooling. The reaction mixture was washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure.
The residue is purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/9), and the obtained solid is washed with n-hexane to give the desired product having a melting point of 92 to 102 ° C. (isomer ratio 14%). : 86) 3.0 g was obtained. The HPLC conditions for analyzing this product were the same as those in Synthesis Example 1 described above. The NMR spectrum data of each geometric isomer is as follows. ¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz) Geometric isomer with shorter retention time: 1.22 (s, 9H), 2.3
4 (s, 3H), 7.02 (d, 2H), 7.19 (d, 2H), 7.33 (d, 1H), 7.42 (t, 1
H), 7.51 (t, 1H), 7.75 (d, 1H) Geometric isomer with a retention time longer than: 1.33 (s, 9H), 2.2
5 (s, 3H), 7.46 (d, 2H), 7.57 (d, 2H), 7.59 (t, 1H), 7.63 (t, 1
H), 7.77 (d, 1H), 7.84 (d, 1H)

Synthesis Example 5 Synthesis of α- (4-tert-butylphenyl) -β-[(methylthio) carbonyloxy] -β- (2-trifluoromethylphenyl) acrylonitrile (isomer ratio 2:98, compound E) SynthesisA mixture of 5.0 g of α- (4-tert-butylphenyl) -β-hydroxy-β- (2-trifluoromethylphenyl) acrylonitrile, 1.5 g of sodium carbonate and 30 ml of methyl ethyl ketone was heated to 70 ° C. Mate 2.
A mixture of 1 g and 10 ml of methyl ethyl ketone was added dropwise over 10 minutes. After completion of the addition, the mixture was reacted at 70 to 75 ° C. for 30 minutes. After cooling the reaction mixture, the inorganic salts were filtered, and the cake was washed with 20 ml of methyl ethyl ketone. The methyl ethyl ketone in the filtrate is distilled off, and an isoparaffinic hydrocarbon (trade name: ISO
(PARG, manufactured by Exxon Chemical) was added, heated and dissolved, and then allowed to cool to room temperature. The precipitated crystals are filtered and the cake is subjected to ISOP
After washing with 10 ml of AR G (trade name), drying at 65 ° C for 12 hours,
4.9 g of the desired product (isomer ratio 2:98) was obtained. The HPLC conditions for analyzing this product are as follows. In addition, N
The MR spectrum data is the same as in Synthesis Example 4. HPLC conditions Stationary phase: Octadecyl-based column (trade name: COSMOSIL 5)
C18-AR-II), 4.6 mm × 250 mm; Nacalai Tesque mobile phase: acetonitrile / 1% H ₃ PO ₄ aqueous solution = 4/1 (V
/ V) Detection wavelength: 254 nm Column temperature: 40 ° C. Flow rate: 1 ml / min

Synthesis Example 6 Synthesis of α- (4-tert-butylphenyl) -β-[(methylthio) carbonyloxy] -β- (2-trifluoromethylphenyl) acrylonitrile (isomer ratio 0: 100, compound F) Heating a mixture of synthesis α- (4-tert-butylphenyl) -β-hydroxy-β- (2-trifluoromethylphenyl) acrylonitrile 5.0 g, sodium carbonate 2.0 g and acetone 30 ml,
Under reflux, a mixture of 2.1 g of methylchlorothiol formate and 10 ml of acetone was added dropwise over 10 minutes. After the completion of the addition, the mixture was reacted under reflux for 60 minutes. After cooling the reaction mixture, the inorganic salts were filtered, and the cake was washed with 20 ml of acetone. Acetone in the filtrate was distilled off, and 50 ml of ISOPAR G (trade name) was added to the residue, heated and dissolved, and allowed to cool to room temperature. The precipitated crystals were filtered, and the cake was washed with ISOPAR G (trade name) 10 ml.
Drying at 12 ° C. for 12 hours gave 4.8 g of the desired product (isomer ratio: 0: 100). The HPLC conditions for analyzing this were the same as in Synthesis Example 5 above. The NMR spectrum data of this is the same as the geometric isomer having a longer retention time of Synthesis Example 4 described above.

Synthesis Example 7 Synthesis of α- (4-chlorophenyl) -β- (S-methyldithiocarbonyloxy) -β- (2-trifluoromethylphenyl) acrylonitrile (isomer ratio 25:75, compound G) 4% 68% sodium hydride and 1 dimethylformamide
50 ml of the mixture is heated to 50-60 ° C., and α- (4
A mixed solution of 33 g of (-chlorophenyl) -β-hydroxy-β- (2-trifluoromethylphenyl) acrylonitrile and 70 ml of dimethylformamide was added dropwise at 55 to 65 ° C. over 1 hour. After the completion of the addition, the mixture was reacted at the same temperature for 30 minutes. Then, the liquid temperature was returned to room temperature. Then, methyl chlorodithioformate 1
2.9 g was added dropwise at 25 ° C. over 15 minutes, and the mixture was reacted for 1.5 hours after completion of the addition. The reaction mixture was poured into 500 ml of ice water and extracted twice with 300 ml of ether. The organic layer was washed with water and saturated saline, and dried over anhydrous magnesium sulfate. To the residue obtained by concentration under reduced pressure, 120 ml of n-pentane was added, and the mixture was heated and stirred, and further stirred for 1 hour under ice cooling to crystallize, to remove the coloring component, and to obtain α- (4-chlorophenyl) having a melting point of 80.8 ° C. ) -β-
(S-methyldithiocarbonyloxy) -β- (2-trifluoromethylphenyl) acrylonitrile (55:45 isomer ratio,
34.6 g of compound H) were obtained. The HPLC conditions for analyzing this product are as follows. HPLC conditions Stationary phase: Octadecyl-based column (trade name: COSMOSIL 5C)
18), 4.6 mm × 150 mm; Nacalai Tesque mobile phase: acetonitrile / water = 3/1 (V / V) Detection wavelength: 254 nm Column temperature: 40 ° C. Flow rate: 1 ml / min

2) α- (4-chlorophenyl) -β- (S-methyldithiocarbonyloxy) -β- (2) having an isomer ratio of 55:45
A solution of 20 g of (trifluoromethylphenyl) acrylonitrile in 1.2 liters of benzene was irradiated with a high-pressure mercury lamp (450 W) at room temperature under a nitrogen gas atmosphere for 2.5 hours. After irradiation, the mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/9) to give the desired product having a melting point of 79.5 ° C. (isomer ratio: 25: 7).
5) 17 g was obtained. The HPLC conditions for analyzing this were the same as in step 1) above. The NMR spectrum data of each geometric isomer is as follows. ^{1 H-NMR δppm (Solvent:} CDCl 3 / 400MHz) having a shorter retention time geometric isomers: 2.58 (s, 3H), 7.0
6 (d, 2H), 7.15 (d, 2H), 7.32 (m, 2H), 7.51 (m, 1H), 7.74 (m, 1
H) Geometric isomer with longer retention time: 2.47 (s, 3H), 7.4
2 (d, 2H), 7.54 (d, 2H), 7.63 (m, 2H), 7.75 (m, 1H), 7.98 (m, 1
H)

Synthesis Example 8 Synthesis of α- (4-chlorophenyl) -β- (S-ethyldithiocarbonyloxy) -β- (2-trifluoromethylphenyl) acrylonitrile (Isomer ratio 28:72, Compound I) ) 60% sodium hydride 68mg and dimethylformamide
A mixed solution of 500 mg of α- (4-chlorophenyl) -β-hydroxy-β- (2-trifluoromethylphenyl) acrylonitrile and 2 ml of dimethylformamide is gradually added dropwise to 10 ml of the mixture under ice-cooling. While the temperature was returned to room temperature, stirring was continued until the generation of hydrogen gas was completed. After that, cool again with ice and ethyl chlorodithioformate 240m
g and 2 ml of dimethylformamide were gradually added dropwise, and after completion of the addition, the mixture was reacted at room temperature for 2 hours. The reaction mixture was poured into 100 ml of ice water, and extracted with 150 ml of ether. The organic layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The residue was subjected to silica gel column chromatography (developing solvent: ethyl acetate /
n-hexane = 1/9), and α- (4-chlorophenyl) -β- (S-ethyldithiocarbonyloxy) -β- (2-trifluoromethylphenyl) acrylonitrile (refractive index n _D ^27.2 1.5612) 380 mg of the compound J) were obtained in an isomer ratio of 52:48. The HPLC conditions under which this product was analyzed were the same as in Synthesis Example 7 above. 2) α- (4-chlorophenyl) -β- (S isomer ratio is 52:48
2-ethyldithiocarbonyloxy) -β- (2-trifluoromethylphenyl) acrylonitrile (2 g) in benzene (100 m)
The solution dissolved in l was irradiated with a high-pressure mercury lamp (100 W) at room temperature under a nitrogen gas atmosphere for 4 hours. After completion of the irradiation, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/9) to obtain the target compound having a melting point of 81.7 ° C. (isomer ratio: 28:72). g was obtained.
The HPLC conditions under which this product was analyzed were the same as in Synthesis Example 7 above. The NMR spectrum data of each geometric isomer is as follows. ^{1 H-NMR δppm (Solvent:} CDCl 3 / 400MHz) having a shorter retention time geometric isomers: 1.23 (t, 3H), 3.0
1 (q, 2H), 7.44 (d, 2H), 7.56 (d, 2H), 7.65 (m, 2H), 7.77 (m, 1
H), geometric isomer with retention time longer than 7.97 (m, 1H): 1.35 (t, 3H), 3.1
4 (q, 2H), 7.07 (d, 2H), 7.19 (d, 2H), 7.29 (m, 2H), 7.49 (m, 1
H), 7.74 (m, 1H)

Synthesis Example 9 Synthesis of α- (4-chlorophenyl) -β- (S-methyldithiocarbonyloxy) -β- (2-trifluoromethylphenyl) acrylonitrile (isomer ratio 0: 100, compound K) 0.8 g of-(4-chlorophenyl) -β-hydroxy-β- (2-trifluoromethylphenyl) acrylonitrile and 1,
8-diazabicyclo [5.4.0] -7-undecene 0.41
g was dissolved in 10 ml of dimethylformamide, and a solution of 0.34 g of methyl chlorodithioformate dissolved in 2 ml of dimethylformamide was added dropwise at room temperature. After completion of the addition, the mixture was reacted at room temperature for 8 hours. The reaction mixture is added to ice water 50
Then, 100 ml of ether was added for extraction. The organic layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 1/9), and the target compound having a melting point of 91.7 ° C. (isomer ratio: 0: 100)
0.2 g was obtained. The HPLC conditions under which this product was analyzed were the same as in Synthesis Example 7 above. The NMR spectrum data is the same as that of the geometric isomer having a longer retention time of Synthesis Example 7 described above.

Reference Synthesis Example 1 Synthesis of α- (4-tert-butylphenyl) -β-hydroxy-β- (2-trifluoromethylphenyl) acrylonitrile 5.8 g of 63% sodium hydride and 137 ml of tetrahydrofuran
Was heated, and 13.5 g of 4-tert-butylbenzyl cyanide and 2-trifluoromethylbenzoyl chloride 1 were added thereto.
A mixture of 5.0 g and 50 ml of tetrahydrofuran was refluxed for 2 hours.
The mixture was added dropwise over a period of time, and reacted at the same temperature for 2 hours after completion of the addition. Tetrahydrofuran in the reaction mixture was distilled off, and 250 ml of water was added to the residue. Thereto, 80 ml of n-hexane was added and washed with stirring for 10 minutes. After standing for 30 minutes, the aqueous layer was separated. 8.3 g of concentrated hydrochloric acid was gradually added dropwise to the aqueous layer with stirring, and the mixture was further stirred for 30 minutes. The precipitated crystals are filtered and water 10
After washing with 0 ml, it was dried at 55 ° C. for 24 hours to obtain 23.7 g of the desired product. The NMR spectrum data of this is as follows. ¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz) 1.36 (S, 9H), 6.42 (S, 1H), 7.52 (d, 2H), 7.57 (d, 2H), 7.62-
7.69 (m, 3H), 7.79 (d, 1H)

Reference Synthesis Example 2 Synthesis of α- (4-tert-butylphenyl) -β-hydroxy-β- (2-trifluoromethylphenyl) acrylonitrile 5.8 g of 63% sodium hydride, 25 ml of tetrahydrofuran and 10 ml of liquid paraffin The mixture was heated, and a mixture of 13.5 g of 4-tert-butylbenzyl cyanide and 15.0 g of 2-trifluoromethylbenzoyl chloride was added dropwise at 65 to 70 ° C. over 2 hours. Was. The reaction mixture was allowed to cool to room temperature, and 250 ml of water was added. Thereto, 80 ml of n-hexane was charged, washed with stirring for 10 minutes, left standing for 30 minutes, and then the aqueous layer was separated. Concentrated hydrochloric acid 8.
After 3 g was gradually added dropwise, the mixture was further stirred for 30 minutes. The precipitated crystals were filtered, washed with 100 ml of water, and dried at 55 ° C. for 24 hours to obtain 23.8 g of the desired product. The NMR spectrum data is the same as in Reference Synthesis Example 1 above.

Reference Synthesis Example 3 Synthesis of α- (4-chlorophenyl) -β-hydroxy-β- (2-trifluoromethylphenyl) acrylonitrile 70 g of potassium tertiary butyrate and tetrahydrofuran 4
A mixture of 45 g of 4-chlorobenzyl cyanide, 62 g of 2-trifluoromethylbenzoyl chloride and 210 ml of tetrahydrofuran was added dropwise to the 50 ml of the mixture at 15 ° C. or lower over 1 hour. Reacted. The reaction mixture was concentrated under reduced pressure, and the residue
And stirred for 15 minutes, followed by washing with 500 ml of methylene chloride. The aqueous layer was adjusted to pH 3 to 4 with concentrated hydrochloric acid, and then methylene chloride 60
The mixture was extracted with 0 ml, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was washed with 300 ml of n-hexane to obtain 87.6 g of the desired product. The NMR spectrum data of this is as follows. ¹ H-NMR δppm (Solvent: CDCl ₃ / 400MHz) 7.41 (d, 2H), 7.58-7.68 (m, 5H), 7.75 (m, 1H)

Reference Synthesis Example 4 Synthesis of α- (4-chlorophenyl) -β-hydroxy-β- (2-trifluoromethylphenyl) acrylonitrile 5.8 g of 4-chlorobenzylcyanide, 10 g of ethyl 2-trifluoromethylbenzoate And 2.9 g of sodium ethylate,
After adding to 100 ml of toluene, the mixture was reacted under reflux for 8 hours.
The reaction mixture was returned to room temperature, and extracted by adding 200 ml of water.
After the aqueous layer was adjusted to pH 6 to 7 with 6N hydrochloric acid, methylene chloride 400 ml
And extracted. The organic layer was washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 6.3 g of the desired product. The NMR spectrum data is the same as in Reference Synthesis Example 3 above.

Next, test examples of the present invention will be described. Test Example 1 A 10% aqueous suspension of each of compound D and compound E was dispersed in water, and a drug solution was prepared so that the active ingredient was 150 ppm.
The chemical was used in the Satsuma mandarin tree (diameter
After spraying using a sprayer on a 24 cm, 29 cm height plastic pot planted), it was left in a greenhouse. Before and 7 days, 12 days, 18 days, and 26 days after the application, the number of adults of the mandarin red mites parasitizing all leaves of the Citrus unshiu tree was examined.
Table 1 shows the results.

[0084]

[Table 1] Table 1

It can be seen from Table 1 that both Compound D and Compound E show an excellent pest control effect, and that Compound E shows a more excellent pest control effect.

Test Example 2 A 10% aqueous suspension of each of compound H and compound G was dispersed in water containing 0.02% of a spreading agent (New Rinault; manufactured by Nippon Agrochemicals Co., Ltd.) so that the active ingredient content became 150 ppm. The solution was adjusted. An eggplant (17 cm in diameter,
Sprayed on a 19 cm-high plastic pot) using a sprayer, and then left in a greenhouse. Before spraying and on days 5, 9, 12, and 15 after spraying, the number of adult spider mites parasitic on eggplant was examined. Table 2 shows the results.

[0087]

[Table 2] Table 2

It can be seen from Table 2 that both Compound H and Compound G exhibit excellent pest control effects, and that Compound G exhibits superior pest control effects.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court II (Reference) // C07M 9:00 C07M 9:00 (72) Inventor Tsuyoshi Ueda 2-3-3 Nishi-Shibukawa, Kusatsu City, Shiga Prefecture No. 1 Ishihara Sangyo Co., Ltd. Central Research Laboratory (72) Inventor Akihiro Hisamatsu 2-3-1 Nishi-Shibukawa, Kusatsu-shi, Shiga Pref. Inside the Central Research Laboratory (72) Inventor Mayumi Kanamori Nishi-Shibukawa 2-chome, Kusatsu-shi, Shiga No.3-1 Ishihara Sangyo Co., Ltd. Central Research Laboratory F-term (reference) 4H006 AA01 AA02 AB02 AC48 AD17 BA02 BA28 BA32 BA51 BA95 BB12 BB16 BB20 BB61 BC10 BC19 BC31 BC34 BC51 QN32 TN60 4H011 AC01 AC04 BA01 BB06 BB12 BC18 DA13 DD03

Claims (13)

[Claims] 1. A compound of the formula (I) Wherein, T is pyridyl substituted with phenyl or R ₂ which is substituted with R _2, Q is phenyl which may be substituted by R _3, which may be thienyl substituted with R _3, substituted by R ₃ Pyridyl or benzyl optionally substituted with R ₃ , R ₁ is —C (＝ O) R ₄ or —C (＝ S) R ₄ , wherein R ₂ and R ₃ are each halogen, Alkyl which may be substituted, alkenyl which may be substituted, alkynyl which may be substituted, alkoxy which may be substituted, alkenyloxy which may be substituted, alkynyloxy which may be substituted, alkylthio which may be substituted Optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkenylthio, optionally substituted alkenylsulfinyl, optionally substituted alkenylsulfinyl Optionally substituted alkynylthio, optionally substituted alkynylsulfinyl, optionally substituted alkynylsulfonyl, nitro, cyano, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylthio , optionally substituted phenylsulfinyl also, optionally substituted phenylsulfonyl, benzyl optionally substituted, optionally substituted benzyloxy, an optionally substituted benzylthio or optionally substituted benzoyl, R ₄ Is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkenyloxy, optionally substituted alkynyloxy, optionally substituted Alkylthio, optionally substituted alkenylthio, substituted Which may be alkynylthio, cycloalkyl, cycloalkyloxy, _{cycloalkylthio, -N (R 5) R 6} , optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylthio, substituted Good benzyl,
Optionally substituted benzyloxy, optionally substituted benzylthio, a -J, -O-J or -S-J, R ₅
And R ₆ are each hydrogen, alkyl or alkoxy, and J is a 5- or 6-membered heterocyclic group containing 1 to 4 at least one heteroatom selected from the group consisting of O, S and N (heterocyclic group Except for the following compounds: (1) T is phenyl substituted with R ₂ , Q is thienyl optionally substituted with R ₃ , and R ₁ is- C (＝ O) R ₄ , wherein R ₄ is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy,
Optionally substituted alkenyloxy, optionally substituted alkynyloxy, cycloalkyl, _{cycloalkyloxy, -N (R 5) R 6} , optionally substituted phenyl, optionally substituted phenoxy, optionally substituted Good phenylthio, optionally substituted benzyl, optionally substituted benzyloxy, optionally substituted benzylthio, -J,-
O-J or compound is -S-J, (2) T is phenyl substituted with R _2, Q is thienyl optionally substituted with R _3, R ₁ is -C (= S) R ₄ and R ₄
There -N (R ₅₎ a R ₆ a compound, (3) T is pyridyl substituted with R _2, Q is a good pyridyl substituted by thienyl which may be substituted or R ₃ in R ₃ A compound wherein R ₁ is —C (＝ O) R ₄ and R ₄ is alkyl; (4) α- (3,5-dimethoxyphenyl) -β-
(2-methoxy-4-methylphenyl) -β-acetoxyacrylonitrile and (5) α- (3,5-dimethoxyphenyl) -β- (2,6-dimethoxy-4-methylphenyl) -β-acetoxyacrylonitrile] Is a geometric isomer of an acrylonitrile-based compound or a salt thereof or a mixture thereof, wherein a filler in which an alkyl group selected from trimethyl, octyl and octadecyl is chemically bonded to silica is used as a stationary phase; A geometric isomer having a longer retention time or a mixture of geometric isomers containing more of the geometric isomer when analyzed by reversed-phase liquid chromatography using a more selected polar solvent as a mobile phase. 2. The geometric isomer mixture according to claim 1, comprising at least 60% of a geometric isomer having a longer retention time. 3. The geometric isomer or the mixture of geometric isomers according to claim 1, wherein the geometric isomer having a longer retention time is E-form. 4. The geometric isomer or the mixture of geometric isomers according to claim 1, wherein the geometric isomer having a longer retention time is a Z-isomer. 5. A compound of the formula (I) Wherein, T is pyridyl substituted with phenyl or R ₂ which is substituted with R _2, Q is phenyl which may be substituted by R _3, which may be thienyl substituted with R _3, substituted by R ₃ Pyridyl or benzyl optionally substituted with R ₃ , R ₁ is —C (＝ O) R ₄ or —C (＝ S) R ₄ , wherein R ₂ and R ₃ are each halogen, Alkyl which may be substituted, alkenyl which may be substituted, alkynyl which may be substituted, alkoxy which may be substituted, alkenyloxy which may be substituted, alkynyloxy which may be substituted, alkylthio which may be substituted Optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkenylthio, optionally substituted alkenylsulfinyl, optionally substituted alkenylsulfinyl Optionally substituted alkynylthio, optionally substituted alkynylsulfinyl, optionally substituted alkynylsulfonyl, nitro, cyano, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylthio , optionally substituted phenylsulfinyl also, optionally substituted phenylsulfonyl, benzyl optionally substituted, optionally substituted benzyloxy, an optionally substituted benzylthio or optionally substituted benzoyl, R ₄ Is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkenyloxy, optionally substituted alkynyloxy, optionally substituted Alkylthio, optionally substituted alkenylthio, substituted Which may be alkynylthio, cycloalkyl, cycloalkyloxy, _{cycloalkylthio, -N (R 5) R 6} , optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylthio, substituted Good benzyl,
Optionally substituted benzyloxy, optionally substituted benzylthio, a -J, -O-J or -S-J, R ₅
And R ₆ are each hydrogen, alkyl or alkoxy, and J is a 5- or 6-membered heterocyclic group containing 1 to 4 at least one heteroatom selected from the group consisting of O, S and N (heterocyclic group Except for the following compounds: (1) T is phenyl substituted with R ₂ , Q is thienyl optionally substituted with R ₃ , and R ₁ is- C (＝ O) R ₄ , wherein R ₄ is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy,
Optionally substituted alkenyloxy, optionally substituted alkynyloxy, cycloalkyl, _{cycloalkyloxy, -N (R 5) R 6} , optionally substituted phenyl, optionally substituted phenoxy, optionally substituted Good phenylthio, optionally substituted benzyl, optionally substituted benzyloxy, optionally substituted benzylthio, -J,-
O-J or compound is -S-J, (2) T is phenyl substituted with R _2, Q is thienyl optionally substituted with R _3, R ₁ is -C (= S) R ₄ and R ₄
There -N (R ₅₎ a R ₆ a compound, (3) T is pyridyl substituted with R _2, Q is a good pyridyl substituted by thienyl which may be substituted or R ₃ in R ₃ A compound wherein R ₁ is —C (＝ O) R ₄ and R ₄ is alkyl; (4) α- (3,5-dimethoxyphenyl) -β-
(2-methoxy-4-methylphenyl) -β-acetoxyacrylonitrile and (5) α- (3,5-dimethoxyphenyl) -β- (2,6-dimethoxy-4-methylphenyl) -β-acetoxyacrylonitrile] Among the acrylonitrile-based compounds represented by or a geometric isomer of a salt thereof or a mixture thereof, using a filler in which an alkyl group selected from trimethyl, octyl and octadecyl is chemically bonded to silica as a stationary phase, from water, methanol and acetonitrile A method for producing a geometric isomer having a longer retention time or a geometric isomer mixture containing a larger amount of the geometric isomer when analyzed by reversed-phase liquid chromatography using a selected polar solvent as a mobile phase,
(A) Formula (II); Wherein T and Q are as defined above, and a compound represented by the formula (III): XR ₁ ... (III) wherein R ₁ is as defined above and X is halogen Is reacted in the presence of a base and a solvent, or (b) a geometric isomer having a shorter retention time when analyzed by the reverse phase liquid chromatography, Isomerizing a mixture of geometric isomers containing more geometric isomers with short retention times under light irradiation,
A method for producing a geometric isomer having the longer retention time or a mixture of geometric isomers containing more of the geometric isomer by any method. 6. A geometric isomer or a mixture of geometric isomers containing more of the geometric isomer produced by the method of claim 5. 7. A compound of the formula (I) Wherein, T is pyridyl substituted with phenyl or R ₂ which is substituted with R _2, Q is phenyl which may be substituted by R _3, which may be thienyl substituted with R _3, substituted by R ₃ Pyridyl or benzyl optionally substituted with R ₃ , R ₁ is —C (＝ O) R ₄ or —C (＝ S) R ₄ , wherein R ₂ and R ₃ are each halogen, Alkyl which may be substituted, alkenyl which may be substituted, alkynyl which may be substituted, alkoxy which may be substituted, alkenyloxy which may be substituted, alkynyloxy which may be substituted, alkylthio which may be substituted Optionally substituted alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted alkenylthio, optionally substituted alkenylsulfinyl, optionally substituted alkenylsulfinyl Optionally substituted alkynylthio, optionally substituted alkynylsulfinyl, optionally substituted alkynylsulfonyl, nitro, cyano, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylthio , optionally substituted phenylsulfinyl also, optionally substituted phenylsulfonyl, benzyl optionally substituted, optionally substituted benzyloxy, an optionally substituted benzylthio or optionally substituted benzoyl, R ₄ Is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkenyloxy, optionally substituted alkynyloxy, optionally substituted Alkylthio, optionally substituted alkenylthio, substituted Which may be alkynylthio, cycloalkyl, cycloalkyloxy, _{cycloalkylthio, -N (R 5) R 6} , optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylthio, substituted Good benzyl,
Optionally substituted benzyloxy, optionally substituted benzylthio, a -J, -O-J or -S-J, R ₅
And R ₆ are each hydrogen, alkyl or alkoxy, and J is a 5- or 6-membered heterocyclic group containing 1 to 4 at least one heteroatom selected from the group consisting of O, S and N (heterocyclic group Except for the following compounds: (1) T is phenyl substituted with R ₂ , Q is thienyl optionally substituted with R ₃ , and R ₁ is- C (＝ O) R ₄ , wherein R ₄ is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy,
Optionally substituted alkenyloxy, optionally substituted alkynyloxy, cycloalkyl, _{cycloalkyloxy, -N (R 5) R 6} , optionally substituted phenyl, optionally substituted phenoxy, optionally substituted Good phenylthio, optionally substituted benzyl, optionally substituted benzyloxy, optionally substituted benzylthio, -J,-
O-J or compound is -S-J, (2) T is phenyl substituted with R _2, Q is thienyl optionally substituted with R _3, R ₁ is -C (= S) R ₄ and R ₄
There -N (R ₅₎ a R ₆ a compound, (3) T is pyridyl substituted with R _2, Q is a good pyridyl substituted by thienyl which may be substituted or R ₃ in R ₃ A compound wherein R ₁ is —C (＝ O) R ₄ and R ₄ is alkyl; (4) α- (3,5-dimethoxyphenyl) -β-
(2-methoxy-4-methylphenyl) -β-acetoxyacrylonitrile and (5) α- (3,5-dimethoxyphenyl) -β- (2,6-dimethoxy-4-methylphenyl) -β-acetoxyacrylonitrile] Among the acrylonitrile-based compounds represented by or a geometric isomer of a salt thereof or a mixture thereof, using a filler in which an alkyl group selected from trimethyl, octyl and octadecyl is chemically bonded to silica as a stationary phase, from water, methanol and acetonitrile A method for producing a geometric isomer having a longer retention time or a geometric isomer mixture containing a larger amount of the geometric isomer when analyzed by reversed-phase liquid chromatography using a selected polar solvent as a mobile phase, formula _{(IV); Q-CH 2} CN ... (IV) wherein, Q is as defined above] is represented by And compounds,
T-COZ (V) wherein T is as described above, and Z is halogen or alkoxy, and reacted with a compound in the presence of a base and a solvent; X-R ₁ ... (III) wherein R ₁ is as described above, and X is a halogen.
A method for producing the geometric isomer having the longer retention time or the geometric isomer mixture containing more of the geometric isomer. 8. A geometric isomer produced by the method of claim 7, or a geometric isomer mixture containing more of the geometric isomer. 9. A compound or a salt thereof, wherein the geometrical isomer of the acrylonitrile compound represented by the formula (I) is E-form. 10. A compound or a salt thereof, wherein the geometrical isomer of the acrylonitrile compound represented by the formula (I) is a Z-isomer. 11. A pesticidal composition comprising the geometric isomer or the mixture of geometric isomers according to claim 1, 9 or 10 as an active ingredient. 12. An insecticide, acaricide or nematicide containing the geometric isomer or the mixture of geometric isomers according to claim 1, 9 or 10 as an active ingredient. 13. A method for controlling pests, which comprises causing the geometric isomer or the mixture of geometric isomers according to claim 1, 9 or 10 to act on pests as an active ingredient.