JPH05230029A - Fluorine-containing pyrazole compound, its production and pest control agent - Google Patents

Abstract

PURPOSE:To provide a new fluorine-containing pyrazole compound useful as a pest control agent such as insecticide or germicide. CONSTITUTION:A fluorine-containing pyrazole compound of formula I (R<1> is H, lover alkyl, benzyl, amino, alkylsulfonyl, phenoxyalkyl, pyridylalkyl, alkoxy, alkoxyalkyl, cycloalkyl, alkinyl, acyl, etc.; R<2> is H, alkyl; R<1> and R<2> are combined with each other to form a nitrogen-containing heterocyclic ring; Q is pyridyl, thienopyridyl, substituted phenyl), e.g. 5-amino-1-(2,6dichrolo-4- trifluoromethylphenyl)-3-pentafluoroethyl-4-trifluoromethylpyrazole. A compound of formula III (R<3> is H, alkyl, benzyl, amino, alkoxy, etc.; R<2> and R<3> are combined with each other to form a nitrogen-containing heterocyclic ring) among the compound of formula I is obtained by reacting a new 3-pentafluoroethyl-4- trifluoromethyl-5-fluoropyrazole with a nucleophilic agent of formula IV.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorine-containing pyrazole compound which is useful as a pest control agent such as insecticides and fungicides.

[0002]

Description of the Prior Art 5-Amino-1-phenyl-3-pentafluoroethyl-4-trifluoromethylpyrazoles are known as fluorine-containing pyrazole compounds, but the 1-position phenyl group is unsubstituted. It is only the body and there is no disclosure of its biological activity [Iz
v. Akad. Nauk SSSR, Ser. Khi
m. , (11) 1990, p. 2583].

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel fluorine-containing pyrazole compound, a process for producing the same, and a synthetic intermediate thereof and a pest control agent containing the compound as an active ingredient.

[0004]

As a result of studies to solve the above-mentioned problems, the present inventors have found that a novel fluorine-containing pyrazole compound has a remarkable controlling activity against pests, and The present inventors have found that 3-pentafluoroethyl-4-trifluoromethyl-5-fluoropyrazoles are useful as raw materials for the production of the above compounds, and have completed the present invention. That is, the present invention is as follows. First
The invention of is represented by the following formula (I):

[0005]

[Chemical 9]

(In the formula, R ¹ is a hydrogen atom, lower alkyl group, benzyl group, amino group, alkylsulfonyl group, phenoxyalkyl group, pyridylalkyl group, alkoxy group, alkoxyalkyl group, lower cycloalkyl group, aminoalkyl group. Represents a lower alkynyl group, a lower haloalkyl group, an alkylthioalkyl group, or an acyl group; R
² represents a hydrogen atom or a lower alkyl group; or R ¹
Represents a nitrogen-containing heterocycle in which R ² and R ² are bonded and cyclized; Q represents a pyridyl group, a thienopyrimidyl group, or a substituted phenyl group. ) Relating to the fluorine-containing pyrazole compound. The second invention is represented by the following formula (II):

[0007]

[Chemical 10]

(In the formula, Q has the same meaning as described above.)
The present invention relates to 3-pentafluoroethyl-4-trifluoromethyl-5-fluoropyrazoles. The third invention is 3-pentafluoroethyl-4-trifluoromethyl- represented by the formula (II) described above.
5-fluoropyrazoles and the following formula (III):

[0009]

[Chemical 11]

(Wherein R ² has the same meaning as in claim 1; R ³ represents a hydrogen atom, a lower alkyl group, a benzyl group, an amino group, an alkylsulfonyl group, a phenoxyalkyl group, a pyridylalkyl group, an alkoxy group. , Alkoxyalkyl group, lower cycloalkyl group, aminoalkyl group,
It represents a lower alkynyl group, a lower haloalkyl group, or an alkylthioalkyl group; or a nitrogen-containing heterocycle in which R ² and R ³ are bonded and cyclized. ) In the above formula (I), characterized by reacting a nucleophile represented by the following formula (IV):

[0011]

[Chemical 12]

The present invention relates to a process for producing a fluorine-containing pyrazole compound represented by the formula (wherein R ² , R ³ and Q have the same meanings as described above). A fourth invention is the following formula (V):

[0013]

[Chemical 13]

(In the formula, Q has the same meaning as described above.)
3-pentafluoroethyl-4-trifluoromethyl-5-aminopyrazole represented by the following formula (VI):

[0015]

[Chemical 14]

In the above formula (I), a compound represented by the formula (R ⁴ represents an acyl group) is reacted with the following formula (VII):

[0017]

[Chemical 15]

The present invention relates to a process for producing a fluorine-containing pyrazole compound represented by the formula (wherein R ⁴ and Q are as defined above). The fifth invention relates to a pest control agent containing the fluorine-containing pyrazole compound represented by the formula (I) as an active ingredient.

The present invention will be described in detail below. Novel Fluorine-Containing Pyrazole Compound [Compound (I) {Compound (IV), Compound (VI
I)}], novel 3-pentafluoroethyl-4-trifluoromethyl-5-fluoropyrazoles [intermediate compound (II)], nucleophile [compound (III)], 3- pentafluoroethyl-4-trifluoromethyl-5-amino pyrazoles [compound (V)], ^R 1 in the compound (VI) [for example, carboxylic acids or reactive compounds thereof, ^{etc.], R 2, R 3, R} 4
And Q are as follows.

R ¹ is a hydrogen atom, a lower alkyl group, a benzyl group, an amino group, an alkylsulfonyl group, a phenoxyalkyl group, a pyridylalkyl group, an alkoxy group, an alkoxyalkyl group, a lower cycloalkyl group, an aminoalkyl group, a lower group. Examples thereof include an alkynyl group, a lower haloalkyl group, an alkylthioalkyl group, an acyl group, and the like, and preferred examples thereof are given below.

A lower alkyl group (for example, having 1 to 10 carbon atoms)
6 straight-chain or branched), preferably straight-chain or branched having 1 to 4 carbon atoms; more preferably straight-chain or branched having 1 to 3 carbon atoms or Branched (eg, methyl, ethyl, propyl, etc.)
Is good.

The benzyl group may be a substituted or unsubstituted phenyl group; preferably a substituted phenyl group is preferred; the substituent group may be a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, iodine atom). Etc.) is preferred; the position of this substituent is preferably the 4-position; and as a more preferred benzyl group,
4-fluorobenzyl group etc. can be mentioned.

Examples of the alkylsulfonyl group include those described as the lower alkyl group above.

Examples of the phenoxyalkyl group include substituted and unsubstituted phenyl groups; examples of the substituent include those described above for the lower alkyl group, and the position of the substituent is at the 2-position. And / or 4-position is preferred; on the other hand, also in alkyl, those described as the lower alkyl group can be mentioned; and more preferred phenoxyalkyl groups are phenoxyethyl group, 2,4-dimethylphenoxyethyl group and the like. Can be mentioned.

The pyridylalkyl group may be a substituted or unsubstituted pyridyl group; on the other hand, the alkyl group may be the one described as the lower alkyl group above; and a more preferable pyridylalkyl group is , 3-pyridylmethyl group and the like.

The alkoxy group has, for example, 1 carbon atom.
To 6 linear or branched ones; preferably linear or branched ones having 1 to 4 carbon atoms; more preferably 1 to 3 carbon atoms A straight-chain or branched one (eg, methoxy group, ethoxy group, propoxy group, etc.) is preferable.

In the alkoxyalkyl group, the alkoxy may be the one described as the above alkoxy group; while, in the alkyl, the one described as the lower alkyl group may be mentioned; and the more preferable alkoxyalkyl group Examples of the group include ethoxyethyl group and methoxypropyl group.

The lower cycloalkyl group has 3 carbon atoms.
To 6 groups (for example, cyclopropyl group, 2-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.);
A cyclopropyl group is preferred.

In the aminoalkyl group, amino has a hydrogen atom as a nitrogen atom and a linear or branched alkyl group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms, more preferably a methyl group). , A straight-chain or branched alkylsulfonyl group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms, more preferably a methyl group). On the other hand, as the alkyl, those mentioned as the lower alkyl group can be mentioned; and more preferable aminoalkyl groups are 2-aminoethyl group and 2-aminoethyl group.
Examples thereof include (N, N-dimethylamino) ethyl group and N- (methanesulfonyl) aminoethyl group.

Examples of the lower alkynyl group include linear or branched ones having 2 to 6 carbon atoms; preferably those having 2 to 4 carbon atoms;
More preferably, a propargyl group is preferable.

In the lower haloalkyl group, the halogen atom (eg, chlorine atom, bromine atom, fluorine atom, iodine atom, etc.) is preferably chlorine atom or fluorine atom; The above-mentioned ones can be mentioned; and more preferable lower haloalkyl groups include a 2-chloroethyl group, a 2,2,2-trifluoroethyl group and the like.

In the alkylthioalkyl group, the alkyl and the alkyl of alkylthio may be the same as those described above for the lower alkyl group for R ¹ ; and the more preferable alkylthioalkyl group is the methylthioethyl group. it can.

As the acyl group, a lower cycloalkylcarbonyl group (having 4 to 7 carbon atoms), an optionally substituted benzoyl group, an optionally substituted pyrazolecarbonyl group (the substituents are, for example, those described above). Examples thereof include those described as the lower alkyl group and those described as the halogen atom above, and lower alkylcarbonyl groups (the lower alkyl group includes those described above as the lower alkyl group). And the like, and more preferable acyl groups are acetyl group, propionyl group, butyryl group, cyclopropanecarbonyl group, benzoyl group, 1,
A 3-dimethyl-4-chloropyrazole-5-carbonyl group and the like can be mentioned.

Examples of R ² include a hydrogen atom and a lower alkyl group; examples of the lower alkyl group include those described above for the lower alkyl group.

The nitrogen-containing heterocycle in which R ¹ and R ² or R ³ and R ² are bonded to each other to form a ring is preferably an imidazole group; more preferably a 1-imidazolyl group.

As Q, a substituted or unsubstituted pyridyl group (the substituent can be, for example, the above-mentioned halogen atom or lower haloalkyl group, and the halogen atom is preferably a chlorine atom. ,
The lower haloalkyl group is preferably a trifluoromethyl group. ), A thienopyrimidyl group (preferably 4-pyrimidyl group), and a substituted phenyl group (the substituent includes, for example, the above-mentioned halogen atom or lower haloalkyl group. And, the halogen atom is preferably A chlorine atom is preferable, and a lower haloalkyl group is preferably a trifluoromethyl group.) A preferable pyridyl group is 3-chloro-5-
Examples thereof include a trifluoromethylpyridin-2-yl group; examples of a preferable thienopyrimidyl group include a thieno (2,3-d) pyrimidin-4-yl group; examples of a preferable substituted phenyl group. Two
-Chloro-4-trifluoromethylphenyl group, 2,6
-Dichloro-4-trifluoromethylphenyl group and the like can be mentioned.

Examples of the reactive compound of the aliphatic carboxylic acid which is the starting compound (VI) used for producing the object compound (I) of the present invention include, for example, acid anhydrides of carboxylic acids corresponding to the aliphatic carboxylic acids. Compounds, acid chlorides or acid bromides, or carboxylic acid esters (carboxylic acid methyl ester, carboxylic acid ethyl ester, carboxylic acid phenyl ester, etc.); preferably carboxylic acid anhydrides or acid chlorides Is good. The compound (I) can be synthesized by the following synthetic method 1 and synthetic method 2.

(Synthesis Method 1) In the synthesis of the compound (IV) in the objective compound (I) of the present invention, the intermediate compound (II) as a starting material and the compound (III) as a nucleophile are usually used in a solvent. , Preferably in the presence of a base.

The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroine, hexane, chlorobenzene, dichlorobenzene, methylene chloride, Chlorinated or unchlorinated aromatics such as chloroform, dichloromethane, dichloroethane, trichloroethylene, cyclohexane, aliphatics,
Alicyclic hydrocarbons; ethers such as diethyl ether, tetrahydrofuran, dioxane, etc .; alcohols such as methanol, ethanol, ethylene glycol, etc. or hydrates thereof; N, N-dimethylformamide, N, N-dimethyl Amides such as acetamide; organic bases such as triethylamine, pyridine, N, N-dimethylaniline; 1,3-dimethyl-2-
Examples thereof include imidazolidinone; dimethyl sulfoxide; a mixture of the above solvents.

The amount of the solvent used may be such that the concentration of the intermediate compound (II) is in the concentration range of 5 to 80% by weight, and preferably the intermediate compound (II) is used. It is preferable to use it in a concentration of 10 to 70% by weight.

Examples of the base include organic bases such as triethylamine, pyridine, 4- (N, N-dimethylamino) pyridine, N, N-dimethylaniline and the like;
Alkali metal alkoxides such as sodium methoxide, sodium ethoxide, etc .; sodium amide,
Examples thereof include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydride and the like.

The amount of the base used can be 0.001 to 5 times by mole with respect to the intermediate compound (II).

The reaction temperature is not particularly limited, but is usually within the temperature range from room temperature to the boiling point of the solvent used or less.
The reaction time varies depending on the above-mentioned concentration and temperature, but is usually 0.1 to 24 hours, preferably 0.1 to 8 hours.

The amount of the raw material compound used is the intermediate compound (I
Compound (III) which is a nucleophile for I) is 0.5 to
The molar ratio is 2 times, but preferably 0.8 to 1.5 times.

3-Pentafluoroethyl-4-trifluoromethyl-5-fluoropyrazoles, which are intermediate compounds (II) of the objective compound (I) of the present invention, include
As described below, it can be produced by reacting perfluoro-2-methyl-2-pentene or the like with arylhydrazine in the presence of a base such as triethylamine.

[0046]

[Chemical 16]

(In the formula, Q has the same meaning as described above.)

As the intermediate compound (II), for example,
Intermediate compounds (II) consisting of the types of substituents corresponding to compounds 1-27 shown in Tables 1 to 4 [Intermediate compounds (II) ₁ to (II) ₂₇ are referred to. And, for example,
The intermediate compound (II) ₁ means that Q in the formula represented by the intermediate compound (II) is a 3-chloro-5-trifluoromethylpyridin-2-yl group. ] Can be mentioned.

Compounds (III) which are not commercially available are described in Org. Syn. Coll. ，
It can be easily synthesized according to the method described in Volume 1, page 119.

Examples of the compound (III) are shown in Table 1.
To each of the compounds (III) consisting of the types of the substituents corresponding to the compounds 1 to 27 [Compound (III) ₁ to
(III) ₂₇ . For example, this compound (II
I) ₁ means that both R ² and R ³ in the formula represented by the compound (III) are hydrogen atoms. ] Can be mentioned.

(Synthesis Method 2) The compound (VII) in the objective compound (I) of the present invention is usually synthesized by reacting the starting compound (V) with the compound (VI) in a solvent in the presence of a base. Can be done by

The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroine, hexane, chlorobenzene, dichlorobenzene, methylene chloride, Chlorinated or unchlorinated aromatics such as chloroform, dichloromethane, dichloroethane, trichloroethylene, cyclohexane, aliphatics,
Alicyclic hydrocarbons; ethers such as diethyl ether, tetrahydrofuran, dioxane, etc .; N, N-
Amides such as dimethylformamide, N, N-dimethylacetamide and the like; triethylamine, pyridine,
Organic bases such as N, N-dimethylaniline;
3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; a mixture of the above solvents, and the like.

The amount of the solvent used may be such that the concentration of the compound (V) is in the range of 5 to 80% by weight, preferably the compound (V).
It is preferable to use it so that the concentration thereof is 10 to 70% by weight.

Examples of the base include organic bases such as triethylamine, pyridine, 4- (N, N-dimethylamino) pyridine, N, N-dimethylaniline and the like;
Alkali metal alkoxides such as sodium methoxide, sodium ethoxide, etc .; sodium amide,
Examples thereof include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydride and the like.

The amount of the base used can be 0.001 to 5 times the molar amount of the compound (V).

The reaction temperature is not particularly limited, but is usually within the temperature range from room temperature to the boiling point of the solvent used,
It is preferable to heat within the temperature range below the boiling point. The reaction time varies depending on the above-mentioned concentration and temperature, but can be usually 0.1 to 24 hours.

The amount of the raw material compound used is 0.5 to 2 times mol of the compound (VI), preferably 0.8 to 1.5 times mol of the compound (V).

The compound (V) can be synthesized by Synthesis Method 1.

Examples of the compound (V) are shown in Tables 4-5.
Compounds (V) [compounds (V) ₂₈ to (V) consisting of the types of substituents corresponding to compounds 28 to 33 shown in
₃₃ . And, for example, the compound (V) ₂₈ means that Q in the formula represented by the compound (V) is a 2,6-dichloro-5-trifluoromethylphenyl group. ] Can be mentioned.

Compound (VI) is, for example, O in the case of an acid chloride of a carboxylic acid corresponding to an aliphatic carboxylic acid.
rg. Syn. Coll. , Vol. 3, p. 169 (1955
Year) and the like.

As the compound (VI), for example, Table 4 to
Each compound (VI) consisting of the kind of each substituent corresponding to the compounds 28 to 33 shown in 5 [Compound (VI) ₂₈ to
(VI) ₃₃ . And, for example, the compound (VI) ₂₈ means that R ^{4 in the} formula represented by the compound (VI) is an acetyl group. ] Can be mentioned.

The desired compound (I) produced as described above is subjected to usual post-treatments such as extraction, concentration and filtration after the completion of the reaction, and if necessary, known methods such as recrystallization and various chromatographies. It can be appropriately purified by the above method.

Examples of the compound (I) are shown in Tables 1 to 5
Each compound (I) consisting of the type of each substituent corresponding to the compounds 1 to 33 shown therein [referred to as compounds 1 to 33]. For example, the compound 1 means that R ¹ and R ² in the formula represented by the compound (I) are hydrogen atoms and Q is a 3-chloro-5-trifluoromethylpyridin-2-yl group. ] Can be mentioned.

The pests which can be controlled by the compound (I) of the present invention include agricultural and horticultural pests [eg, Hemiptera (Plants, leafhoppers, aphids, whiteflies, etc.), Lepidoptera (Beetle beetles). , Diamondback moth, leaf beetle, leaf moth, scabbard beetle, etc.), Coleoptera (Galloridae, Weevil, Chrysomelidae, Chafer, etc.) )], Sanitary pests (for example, flies, mosquitoes, cockroaches, etc.), stored-grain pests (Beetle beetles, bean weevils, etc.), root-knot nematodes, pine wood nematodes, mite, and the like. For example, wheat leaf rust, barley powdery mildew, cucumber bean sickness, rice blast, toma Epidemics, etc.) can be mentioned.

The pest control agent of the present invention is used for remarkable insecticidal
It has acaricidal and bactericidal effects and contains one or more compounds (I) as active ingredients. Compound (I)
Can be used alone, but is usually mixed with a carrier, a surfactant, a dispersant, an auxiliary agent, etc. by a conventional method (for example, powders, emulsions, fine granules, granules, wettable powders, oily preparations). (Prepared as a composition such as a suspension or an aerosol) is preferably used.

As the carrier, for example, solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic carbonization Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene) Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethylsulfoxide, etc.), water; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection) out and the like.

Surfactants and dispersants that can be used to improve the performance of the present agent such as adhesion to animals and plants, improvement of absorption, dispersion of drug, emulsification, spreading and the like include, for example, alcohol sulfates and alkyls. Examples thereof include sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like. In order to improve the properties of the preparation, for example, carboxymethyl cellulose, polyethylene glycol, gum arabic or the like can be used as an auxiliary agent.

In the production of the present agent, the above-mentioned carrier, surfactant, dispersant and auxiliary agent can be used alone or in suitable combination according to the purpose.
The concentration of the active ingredient in the case where the compound (I) of the present invention is formulated is usually 1 to 50% by weight in an emulsion and 0.3 in a powder.
25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, usually 0.5 to 5% by weight for oils, usually 0.1 to 5% by weight for aerosols. is there.

These preparations can be diluted to an appropriate concentration and sprayed on the plant foliage, soil, water surface of paddy fields or directly applied for various purposes according to the purpose.

[0070]

EXAMPLES Examples of the present invention will be specifically described below.
It should be noted that these examples do not limit the scope of the present invention. Example 1 [Synthesis of Intermediate Compound (II)]

(1) Synthesis of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-fluoro-3-pentafluoroethyl-4-trifluoromethylpyrazole [intermediate compound (II) ₃ ] Perfluoro-2-methyl-2-pentene (42.9
g) was dissolved in N, N-dimethylformamide (350 ml) and cooled with a dry ice-acetone bath to give 2,6-
Dichloro-4-trifluoromethylphenylhydrazine (35 g) was added, and triethylamine (66.
5 ml) was added dropwise. After reacting for 15 minutes, 1 more at room temperature
Stir for hours. After the reaction, the reaction mixture was poured into water and extracted with toluene. The toluene layer was washed with water and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was subjected to column chromatography (Wako gel C200, eluted with hexane), and the obtained oily substance was distilled under reduced pressure to give 1
2 g was obtained.

Colorless oil b. p. 104-106 ° C / 4 mmHg CI- Mass (m / z) 485 (M ⁺ +1), 41
5 (M ⁺ -69)

(2) According to the same method as the above (1),
The intermediate compound (II) was obtained. 1- (2-chloro-4-trifluoromethylphenyl) -5-fluoro-3-pentafluoroethyl-4-
Trifluoromethylpyrazole [Intermediate compound (II)
₁₉ ]

Colorless oil CI-Mass (m / z) 451 (M ⁺ +1), 19
5 (M ⁺ -255)

1- (3-chloro-5-trifluoromethylpyridin-2-yl) -5-fluoro-3-pentafluoroethyl-4-trifluoromethylpyrazole [intermediate compound (II) ₁ ]

Colorless oil CI-Mass (m / z) 452 (M ⁺ +1), 38
2 (M ⁺ -69)

1- [thieno (2,3-d) pyrimidin-4-yl] -5-fluoro-3-pentafluoroethyl-4-trifluoromethylpyrazole [intermediate compound (II) ₄ ]

Colorless oil CI-Mass (m / z) 407 (M ⁺ +1)

Example 2 [Synthesis of Compound (I)] (1) 5-Amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-pentafluoroethyl-4-trifluoromethylpyrazole Synthesis of (Compound 3) The target compound (IV) was synthesized by Synthesis Method 1. 1
-(2,6-Dichloro-4-trifluoromethylphenyl) -5-fluoro-3-pentafluoroethyl-4-
Trifluoromethylpyrazole (3 g) was dissolved in tetrahydrofuran (20 ml), and 28% aqueous ammonia (5 ml) was added. Approximately 80 ° C of this mixture in a sealed tube
Heated for 3 hours. After the reaction, the target compound was extracted from this reaction mixture with toluene, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oily substance was crystallized from hexane to obtain 1.5 g of the target compound as colorless crystals.

(2) 5-ethylamino-1- (2,6-
Synthesis of dichloro-4-trifluoromethylphenyl) -3-pentafluoroethyl-4-trifluoromethylpyrazole (Compound 14) According to Synthesis Method 1, the target compound (IV) was synthesized. 1
-(2,6-Dichloro-4-trifluoromethylphenyl) -5-fluoro-3-pentafluoroethyl-4-
Trifluoromethylpyrazole (0.7 g), ethylamine hydrochloride (0.2 g), triethylamine (1 ml)
Was suspended in N, N-dimethylformamide (5 ml),
The mixture was stirred at room temperature for 1 hour. After the reaction, the target compound was extracted from this reaction mixture with toluene, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oily substance was purified by column chromatography (Wakogel C-200, elution with hexane: toluene = 1: 1) to obtain 0.4 g of the target compound as colorless crystals.

(3) 5-propionylamino-1-
Synthesis of (2,6-dichloro-4-trifluoromethylphenyl) -3-pentafluoroethyl-4-trifluoromethylpyrazole (Compound 31) The target compound (VII) was synthesized by Synthesis Method 2.
5-Amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-pentafluoroethyl-4-
Trifluoromethylpyrazole (0.7 g) and triethylamine (1 ml) were dissolved in toluene and stirred at room temperature.
A toluene solution (3 ml) of propionyl chloride (0.3 g) was gradually added. To this solution, a catalytic amount of 4-
(N, N-dimethylamino) pyridine was added, and the temperature was about 50 °.
Stirred at C for 3 hours. After the reaction, the target compound was extracted from this reaction mixture with toluene, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oily substance was subjected to column chromatography (Wako Gel C-2
00, toluene: AcOEt = 15: 1 elution) to obtain 0.3 g of the target compound as colorless crystals.

(4) Other compounds shown in Tables 1 to 5 were synthesized according to the synthetic methods (1) to (3) above.

[0083]

[Table 1]

[0084]

[Table 2]

[0085]

[Table 3]

[0086]

[Table 4]

[0087]

[Table 5]

Example 3 [Preparation of preparation] (1) Preparation of granules 5 parts by weight of compound 1, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of neoperex powder (trade name; manufactured by Kao Corporation) And 2 parts by weight of sodium lignin sulfonate were uniformly mixed, and then a small amount of water was added and kneaded, then granulated and dried to obtain a granule.

(2) Preparation of wettable powder 10 parts by weight of compound 1, 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of neoperex powder (trade name; manufactured by Kao Corporation) and demol (product) Name; manufactured by Kao Co., Ltd.)
Then, it was pulverized to obtain a wettable powder.

(3) Preparation of emulsion To 20 parts by weight of compound 1 and 70 parts by weight of xylene, 10 parts by weight of toxanone (trade name; manufactured by Sanyo Kasei Co., Ltd.) were added and uniformly mixed and dissolved to obtain an emulsion. ..

(4) Preparation of Dust Preparation 5 parts by weight of compound 1, 50 parts by weight of talc and 4 of kaolin
A powder was obtained by uniformly mixing 5 parts by weight.

Example 4 [Efficacy test] (1) Efficacy test against brown planthopper Compounds (I) shown in Tables 1 to 5 prepared according to Example 3
30% of each wettable powder of water with surfactant (0.01%)
Dilute it to 0 ppm and add 30 seedlings of rice to each of these chemicals.
It was dipped for 2 seconds, air-dried, and then inserted into each glass cylinder. Next, 10 glass larvae of the 3rd instar were released into each of these glass cylinders, covered with a porous lid, and allowed to stand in a constant temperature room at 25 ° C, and after 4 days, the number of live and dead larvae in each glass cylinder was counted and killed. I asked for the rate.

The insecticidal effect is evaluated in four stages (A: 100%, B: 99-80%, C: 7) depending on the range of mortality.
9-60%, D: 59% or less). Note that Iz
v. Akad. Nauk SSSR, Ser. Khi
m. , (11) 1990, p. 2583

[0094]

[Chemical 17]

The results obtained by investigating the same efficacy test using a comparative preparation containing the same as the above were used as a comparative example. The results are shown in Table 6.

[0096]

[Table 6]

(2) Efficacy test against Pleurotus ostreatus Compound (I) shown in Tables 1 to 5 prepared according to Example 3
Each of the wettable powders in 1 was diluted to 500 ppm with water containing a surfactant (0.01%), and 1 ml of each of these chemicals was applied to a filter paper (diameter 7.8 cm, 1 sheet) in each plastic cup. It was dripped onto and air dried. 1 in each of these cups
The number of dead larvae was calculated by counting the number of live and dead larvae in each cup after leaving 0 capillaris (adults) and leaving them in a constant temperature room at 25 ° C. The results of evaluation of the insecticidal effect are shown in Table 7 by the four-step evaluation method described in (1) above, together with the comparative examples obtained by using the comparative preparation described in (1) above.

[0098]

[Table 7]

(3) Control efficacy test against cucumber bean and disease (preventive effect) One cucumber (cultivar; Sagamihanjiro) was grown in a plastic flower pot with a diameter of 6 cm and seedlings at 1.5 leaf stage In addition, the wettable powder prepared from Compound (I) shown in Tables 1 to 5 according to Example 3 was diluted to 500 ppm with water containing a surfactant (0.01%), and 20 ml per pot was prepared.
It was sprayed with. After spraying, it is cultivated in a glass greenhouse for 2 days, and then cucumber and disease fungus (Pseudoperonosp)
Ora cubensis) zoosporangium was prepared from diseased leaves, and this was uniformly spray-inoculated on the back surface of plant leaves. After inoculation, the mixture was kept in the dark at 20 ° C. for 2 days and then grown in a glass greenhouse for 5 days to examine the degree of cucumber bean and lesions appearing on the first leaf.

The bactericidal effect was evaluated in 6 levels (0: whole diseased, 1: lesion area was about 60%, 2: lesion area was about 40%, as compared with the degree of lesions in the untreated section. 3: The lesion area is about 20%, 4: The lesion area is 10% or less, and 5: No lesion). The results are shown in Table 8. The results are shown in Table 8.

[0101]

[Table 8]

[0102]

The novel fluorine-containing pyrazole compound of the present invention is a pesticide useful as a pest control agent.

[Chemical 8]

Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical indication location C07D 495/04 105 Z 9164-4C (72) Inventor Kiyoshi Shitsuchi 5 1978, Ube, Yamaguchi Prefecture Ube Industries Ube Institute Co., Ltd.

Claims (5)

[Claims] 1. The following formula: (In the formula, R ¹ is a hydrogen atom, a lower alkyl group, a benzyl group, an amino group, an alkylsulfonyl group, a phenoxyalkyl group, a pyridylalkyl group, an alkoxy group, an alkoxyalkyl group, a lower cycloalkyl group, an aminoalkyl group, a lower alkynyl. Group, a lower haloalkyl group, an alkylthioalkyl group, or an acyl group; R ² represents a hydrogen atom, or a lower alkyl group; or R ¹ and R ² represent a nitrogen-containing heterocycle in which R ¹ and R ² are bonded to each other; Is a pyridyl group,
Represents a thienopyrimidyl group or a substituted phenyl group. ) A fluorine-containing pyrazole compound represented by 2. (In the formula, Q has the same meaning as described in claim 1.) 3-Pentafluoroethyl-4-trifluoromethyl-5-fluoropyrazoles. 3. A compound represented by formula (II) according to claim 2
-Pentafluoroethyl-4-trifluoromethyl-5
-Fluoropyrazoles and the following formula: (In the formula, R ² has the same meaning as described in claim 1; R ³ represents a hydrogen atom, a lower alkyl group, a benzyl group, an amino group, an alkylsulfonyl group, a phenoxyalkyl group, a pyridylalkyl group, an alkoxy group, an alkoxyalkyl. Group, a lower cycloalkyl group, an aminoalkyl group, a lower alkynyl group, a lower haloalkyl group, or an alkylthioalkyl group; or R ² and R ³ represent a bonded and cyclized nitrogen-containing heterocycle. In the formula (I) according to claim 1, wherein a nucleophile is reacted, the following formula: (In the formula, R ² and Q have the same meanings as defined in claim 1;
³ has the same meaning as described above. The manufacturing method of the fluorine-containing pyrazole compound shown by these. 4. The following formula: (Wherein Q has the same meaning as in claim 1) and 3-pentafluoroethyl-4-trifluoromethyl-5-aminopyrazoles and the following formula: (Wherein R ⁴ represents an acyl group) is reacted with a compound represented by the following formula: (Q has the same meaning as described in claim 1; R ⁴ has the same meaning as described above.) A process for producing a fluorine-containing pyrazole compound. 5. A pest control agent containing the fluorine-containing pyrazole compound represented by the formula (I) according to claim 1 as an active ingredient.