JPH06199805A - Production of @(3754/24)3-substituted phenyl)pyrazole derivative - Google Patents

Abstract

(57) [Summary] [Structure] A method for producing a 3- (substituted phenyl) pyrazole derivative of the formula (I), which comprises halogenating a pyrazole of the formula (II) in the presence of a halogenating agent. . [Chemical 1] (Wherein R ¹ is H, lower alkyl; R ² is lower alkoxy,
Lower haloalkoxy; R ³ is halogen, lower alkoxy,
Carboxyl, lower alkoxycarbonyl, lower alkylthiocarbonylalkoxycarbonyl, aminocarbonylalkoxy, lower alkoxycarbonylalkoxy; X and Y represent halogen. )

Description

Detailed Description of the Invention

[0001]

The present invention relates to the general formula (I)

[Chemical 3] [In the formula, R ¹ represents a hydrogen atom or a lower alkyl group, R ² represents a lower alkoxy group or a lower haloalkoxy group, and R ³
Is a halogen atom, a lower alkoxy group, a carboxyl group,
A lower alkoxycarbonyl group, a lower alkylthiocarbonylalkoxycarbonyl group, an aminocarbonylalkoxy group or a lower alkoxycarbonylalkoxy group, X represents a halogen atom which may be the same or different,
Y represents a halogen atom. ] It is related with the manufacturing method of the 3- (substituted phenyl) pyrazole derivative represented by these.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication No. 2-300173 and Japanese Unexamined Patent Publication No.
47180, JP-A-3-81275, JP-A3-1.
3- (Substituted phenyl) obtained by the production method of the present invention, such as 51367 and JP-A-3-163063.
It is disclosed that the pyrazole derivative is useful as a herbicide.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have completed the present invention as a result of extensive research on a novel method for producing a 3- (substituted phenyl) pyrazole derivative useful as a herbicide. Is.

[0004]

A method for producing a 3-substituted phenylpyrazole derivative represented by the general formula (I) of the present invention is shown schematically, for example, as follows.

[Chemical 4] [In the formula, R ¹ , R ² , R ³ , X and Y are the same as defined above. ]

The pyrazoles represented by the general formula (II) are halogenated with a halogenating agent in the presence or absence of an inert solvent to give 3- (substituted) represented by the general formula (I). Phenyl) pyrazole derivatives can be prepared. The inert solvent that can be used in this reaction may be any one that does not significantly inhibit the progress of this reaction, for example, methylene chloride,
Halogenated hydrocarbons such as chloroform and carbon tetrachloride,
Aromatic hydrocarbons such as benzene, toluene, xylene,
Chain ethers such as diethyl ether and methyl cellosolve, cyclic ethers such as dioxane and tetrahydrofuran, organic acids such as acetic acid, sulfolane, dimethyl sulfoxide, N, N-dimethylformamide, phosphorus oxychloride, water and the like. Can be used, and these inert solvents can be used alone or as a mixture, but the present invention is not limited to these inert solvents.

The halogenating agent used in the present invention includes
For example, halogenating agents such as chlorine, bromine, iodine, sulfuryl chloride, phosphorus pentachloride, phosphorus pentabromide and sodium hypochlorite can be used, and these halogenating agents can be used alone or in a mixture. It can also be used. The amount of the halogenating agent to be used may be selected and used in the range of from equimolar to excess molar with respect to the pyrazoles represented by the general formula (II), and preferably a slight excess is used. A catalytic amount of iron powder, potassium iodide, iodine or the like may be added to accelerate the progress of this reaction.

This reaction can also be carried out in the presence of a dehydrohalogenating agent, and as the dehydrohalogenating agent,
For example, an inorganic base such as sodium acetate, potassium acetate, sodium hydrogen carbonate, potassium hydrogen carbonate or the like can be used. The amount to be used may be selected and used in the range of equimolar to excess molar with respect to the pyrazoles represented by the general formula (II).

The reaction temperature of this reaction may be appropriately selected from room temperature to the boiling point range of the inert solvent used. The reaction time varies depending on the reaction amount, reaction temperature, etc., but is in the range of several minutes to 48 hours. After the completion of the reaction, the desired product can be produced by isolating it from the reaction system containing the desired product by a conventional method and purifying it if necessary. The pyrazoles represented by the general formula (II), which are the starting compounds of the 3- (substituted phenyl) pyrazole derivative represented by the general formula (I) of the present invention, are produced, for example, by the production method illustrated below. can do.

[0009].

[Chemical 5] [In the formula, R ¹ , R ² and X are the same as defined above, R ^3-1 represents a halogen atom or a lower alkoxy group, R ² 'represents a lower alkyl group or a lower haloalkyl group, and R ⁵ represents a lower alkyl group. A group or a lower alkylthiocarbonylalkyl group,
Z represents a halogen atom. ]

When R ³ is a halogen atom, a lower alkoxy group, a carboxyl group, a lower alkoxycarbonyl group or a lower alkylthiocarbonylalkoxycarbonyl group,
A compound represented by the general formula (XIV) is reacted with a hydrazine represented by the general formula (V) to give a compound represented by the general formula (XIII), and the compound (XIII) is isolated or isolated. Alternatively, the pyrazoles represented by the general formula (II-1) can be produced by reacting with the halides represented by the general formula (III). Then represented by the obtained formula (II-1) pyrazole - pyrazole which R ^{3 1} Le class is represented by a halogen atom -
The pyrazoles represented by the general formula (II-2) can be produced by carboxylating the phenols. Further, the pyrazoles represented by the general formula (II-3) can be produced by subjecting the pyrazoles (II-2) to an esterification reaction.

The general formula (II) obtained by the production method shown in Table 1
Typical examples of pyrazoles represented by General formula (II)

[Chemical 6]

[0012]

[Table 1]

Table 2 shows the NMR data of the compounds whose physical properties are shown in Table 1 as viscous substances.

[Table 2]

[0014].

[Chemical 7] [Wherein R ¹ , R ² ′, R ⁴ , X and Z are the same as defined above, and R ⁶
Represents a lower alkoxy group or amino group, and M represents an alkali metal atom. ]

When R ⁶ is an aminocarbonylalkoxy group or a lower alkoxycarbonylalkoxy group, the general formula (X
II) and the halides represented by the general formula (XI) are converted to compounds represented by the general formula (X) by Friedel-Crafts reaction, and the compound (X) is isolated or isolated. Without reacting with the cyanide of the alkali metal atom represented by the general formula (IX) to give a compound represented by the general formula (VIII), the compound (VIII) is isolated or acidified without isolation. A compound represented by the general formula (VI) is obtained by reacting with an alcohol represented by the general formula (VII) below, and the compound (VI) is isolated or not isolated and the compound represented by the general formula (V) To a compound represented by the general formula (IV) by reacting with a hydrazine represented by the general formula (IV) with or without isolation of the compound (IV)
The pyrazoles represented by the general formula (II-4) can be produced by reacting with the halides represented by (III).

General formula (II) obtained by the production method shown in Table 3
Typical examples of pyrazoles represented by General formula (II)

[Chemical 8]

[0017]

[Table 3]

Table 4 shows the NMR data of the compounds whose physical properties are shown in Table 3 as viscous substances.

[Table 4]

[0019]

EXAMPLES Representative examples of the present invention will be illustrated below, but the present invention is not limited thereto.

Example 1 Preparation of 3- (5-bromo-2,4-dichlorophenyl) -4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazole (No. 1)

[Chemical 9] 3- (5-bromo-2,4-dichlorophenyl) -5-
Difluoromethoxy-1-methyl-1H-pyrazole 3.30 g (8.87 mmol), phosphorus oxychloride 20
A mixture of ml and 2.22 g (10.6 mmol) of phosphorus pentachloride was reacted under reflux for 7 hours. After the reaction was completed, phosphorus oxychloride was distilled off under reduced pressure, ice water (20 ml) was added to the residue, and the desired product was extracted with ethyl acetate.
The solution was washed successively with aqueous sodium hydrogen carbonate, water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 3.52 g of the desired product. Physical property: mp78.8 ° C Yield: 97.6%

Example 2 4-chloro-3- (4-chloro-2-fluoro-5-isopropoxyphenyl) -5-
Production of difluoromethoxy-1-methyl-1H-pyrazole (No7)

[Chemical 10] 3- (4-chloro-2-fluoro-5-isopropoxyphenyl) -5-difluoromethoxy-1-methyl-1
After dissolving 6.69 g (20 mmol) of H-pyrazole in 20 ml of carbon tetrachloride, 3.0 g of sulfuryl chloride was added.
(22 mmol) was added dropwise at room temperature, and the reaction was carried out at room temperature for 2 hours after the completion of the addition. After the reaction is completed, the reaction solution is treated with 20 m of water.
The target substance was extracted with dichloromethane, the dichloromethane layer was washed with water, washed with 5% aqueous sodium hydrogen carbonate to neutralize, washed with water and saturated brine in that order, dried over anhydrous magnesium sulfate, and then the solvent was added. It was distilled off under reduced pressure to obtain 7.01 g of the pasty target product. Physical properties: nD1.5376 (22.1 ° C) Yield 95% Similarly, 4-chloro-3- (4-chloro-2-fluoro-5-methoxyphenyl) -5-difluoromethoxy-1-methyl-1H- Pyrazol was produced (No4). Physical property: mp91.7 ° C Yield: 89%

Example 3 2- [2-chloro-4-fluoro-5- (4-chloro-5-difluoromethoxy-1-)
Methyl-1H-pyrazol-3-yl) phenoxy] acetic acid amide production (No 14)

[Chemical 11] 2- [2-chloro-4-fluoro-5- (5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) phenoxy] acetic acid amide (1.40 g, 4.0 mmol) was added to glacial acetic acid (20 ml). And chlorine gas was blown into the solution at room temperature for 3 minutes. After the reaction is complete, add 1
00 ml was added, the target product was extracted with ethyl acetate, the organic layer was washed with an aqueous solution of sodium thiosulfate, water and saturated brine in that order, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 1.39 g of the desired product. Physical properties: mp158.0-160.5 ° C Yield: 90.
5%

Example 4 2- [2-chloro-4-fluoro-5- (4-chloro-5-difluoromethoxy-1-)
Methyl-1H-pyrazol-3-yl) phenoxy] ethyl acetate production (No 16)

[Chemical 12] Ethyl 2- [2-chloro-4-fluoro-5- (5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) phenoxy] acetate 1.80 g (4.75 mmol) ethyl acetate in 50 ml dichloromethane. After dissolution, 0.80 g (5.92 mmol) of sulfuryl chloride was added dropwise to the solution at room temperature, and the reaction was performed at room temperature for 2 hours after the completion of the addition.
After the completion of the reaction, 100 ml of water was added to the reaction solution, the desired product was extracted with dichloromethane, the organic layer was washed with water, neutralized with 5% aqueous sodium hydrogen carbonate, washed with water and saturated brine, and dried over magnesium sulfate, The solvent was distilled off under reduced pressure to obtain 1.70 g of crude crystals of the desired product. The crude crystals obtained were purified by silica gel column chromatography to obtain 1.09 g of the desired product. Physical property: mp127.6 ° C Yield: 56%

Example 5 2- [2-chloro-4-fluoro-5- (4-chloro-5-difluoromethoxy-1-)
Production of methyl-1H-pyrazol-3-yl) phenoxy] acetic acid (No 19)

[Chemical 13] 2- [2-chloro-5- (5-difluoromethoxy-1
-Methyl-1H-pyrazol-3-yl) phenoxy]
5 g (14.2 mmol) of acetic acid was dissolved in 20 ml of N, N-dimethylformamide, and 17.7 g (28.4 mmol) of 12% aqueous sodium hypochlorite solution was added dropwise to the solution at 40 ° C. The reaction was carried out at 40 ° C for 1 hour. After completion of the reaction, 25 ml of water was added to the reaction solution, and crystals precipitated by acidification with 6N hydrochloric acid were filtered under reduced pressure, washed with water and dried under reduced pressure to obtain 5.29 g of the desired product. Physical property: mp141.5 ° C Yield: 96%

General formulas obtained in the same manner as in the examples below
The 5- (substituted phenyl) pyrazole derivative represented by (I) is shown in Table 5, but the present invention is not limited thereto. General formula (I)

[Chemical 14]

[0026]

[Table 5]

Table 6 shows the NMR data of the compounds whose physical properties are shown in Table 5 as viscous substances.

[Table 6]

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hiroshi Hamaguchi 10-1, Fukakusa-Horitacho, Fushimi-ku, Kyoto-shi, Kyoto A-804

Claims (1)

[Claims] 1. A compound represented by the general formula (II): [In the formula, R ¹ represents a hydrogen atom or a lower alkyl group, R ² represents a lower alkoxy group or a lower haloalkoxy group, and R ³
Is a halogen atom, a lower alkoxy group, a carboxyl group,
It represents a lower alkoxycarbonyl group, a lower alkylthiocarbonylalkoxycarbonyl group, an aminocarbonylalkoxy group or a lower alkoxycarbonylalkoxy group, and X represents a halogen atom which may be the same or different. ] The pyrazoles represented by the formula [I] are characterized in that they are halogenated in the presence of a halogenating agent. [In the formula, R ¹ , R ² , R ³ and X are the same as defined above, and Y represents a halogen atom. ] The manufacturing method of the 3- (substituted phenyl) pyrazole derivative represented by these.