JPH0369904B2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to the general formula () [In the formula, X represents a halogen atom, and n represents 1 or 2. ] The present invention relates to a sulfate of a novel triazolyl styryl ketone derivative represented by the following.

The triazolyl styryl ketone derivative represented by the general formula () is itself advantageous as a bactericide (Japanese Unexamined Patent Publication No. 130661/1983), but the general formula () obtained by reducing it is [In the formula, X and n have the same meanings as above. ] The triazolylstyryl carbinol derivative represented by is useful as a fungicide, herbicide and/or plant growth regulator, and its E form is known to be more effective than its Z form. (Japanese Patent Application Laid-open Nos. 54-41875, 55-124771, 56-25105).

The triazolyl styryl ketone derivative can be produced by several methods (Japanese Unexamined Patent Application Publication No. 130661/1989, etc.), but generally, the triazolyl styryl ketone derivative obtained by these methods is free of impurities. It often contains , and its purification is also difficult.

As a result of extensive studies, the present inventors have found that the sulfate of the triazolyl styryl ketone derivative represented by the above general formula () is an important intermediate in purifying the above triazolyl styryl ketone derivative. Furthermore, it was discovered that the E-form and Z-form, which had been considered difficult in the past, could be efficiently and easily separated by passing through the sulfate.

That is, by reacting the triazolyl styryl ketone derivative represented by the general formula () with sulfuric acid, a highly purified sulfate is formed, and after the sulfate is separated and obtained, it is decomposed to obtain a highly purified A pure triazolyl styryl ketone derivative represented by the general formula () is obtained.

Further, since the sulfate of the E form and the sulfate of the Z form have different solubility in a solvent, the E form and the Z form can be separated by utilizing this difference in solubility.

The present invention will be explained below.

As the triazolyl styryl ketone derivative represented by the general formula (), the substituent on the phenyl nucleus is
Xn is 4-chlor, 4-bromo, 4-fluoro,
These derivatives include 2-fluoro-4-chlor and 2,4-dichlor, and the 2,4-dichlor and 4-chlor derivatives are particularly important from the viewpoint of their physiological activity.

As a method for producing the sulfate of a triazolyl styryl ketone derivative of the present invention, (i) a mixture of E form and Z form (hereinafter referred to as E/Z form) and sulfuric acid in an equimolar or more amount are preferably seeded. (E/Z-form sulfate) By reacting in an inert solvent in the presence of E/Z-form sulfate, the E/Z-form sulfate can be easily obtained as a crystal. (ii) E-form sulfate and Z-form sulfate are
Either the E and Z forms are reacted with sulfuric acid in an inert solvent to obtain the respective sulfates as crystals, or (iii) the E/Z forms are reacted with each other, such as the 2,4-dichlor form. By adding sulfuric acid in an aprotic solvent, the E-form sulfate that precipitates first is separated, and the Z-form sulfate can also be obtained by adding sulfuric acid to the remaining solution.

To recover the ketone body from the sulfate of the present invention, usually in the presence of a solvent that is immiscible with water and dissolves the ketone body, such as toluene, monochlorobenzene, ethyl acetate, methyl isobutyl ketone, ether, etc. By mixing a large excess of water with the sulfate, the sulfate is decomposed and purified ketone bodies are recovered from the oil layer. At this time, a base such as sodium carbonate, sodium bicarbonate, sodium hydroxide, or ammonia may be present in water in excess of sulfuric acid. In addition to water, the sulfate can be decomposed using an excessive amount of water-containing protic solvents such as methanol or acetic acid, or bases such as amines.

The present invention will be explained below with reference to examples and reference examples, but the present invention is not limited to these examples. Note that E/Z represents the ratio of E-form and Z-form.

Example 1 1 g of Z isomer of 2,4-dichlor is added to 10 g of toluene.
0.083cc of concentrated sulfuric acid while stirring at 20℃
added. Thereafter, it was cooled to 12° C. and collected after 6 hours. The crystals were washed with a small amount of toluene and dried under vacuum.

Yield 0.62g Melting point 117.5-118℃ Elemental analysis amount C(%) H(%) N(%) 43.0 4.2 9.9 Elemental analysis amount S(%) Cl(%) 7.4 17.1 Example 2 4-chlor form of Z 0.3 g of sulfuric acid was dissolved in 3 g of toluene, and 0.1 g of sulfuric acid was added while stirring at 20°C.
After 6 hours, the crystals were collected, washed with a small amount of toluene, and then dried in vacuum.

Yield 0.338g Melting point 68-80.5℃ Elemental analysis amount C(%) H(%) N(%) 45.5 4.7 9.8 Elemental analysis amount S(%) Cl(%) 9.7 8.4 Example 3 2,4-dichlor compound 1g of E-form of 10g of toluene
Dissolved in 0.165% of concentrated sulfuric acid, kept warm at 20℃, and stirred
cc was added. The mixture was stirred for 2 hours and then filtered. After washing the crystals with a small amount of toluene, the crystals were vacuum dried.

Crystal yield 1.27g Melting point 205.5-207℃ Elemental analysis amount C(%) H(%) N(%) 42.8 4.1 9.8 Elemental analysis amount S(%) Cl(%) 7.5 16.9 Example 4 E of 4-chlor form 1 g of the solution was dissolved in 10 g of toluene, and 0.092 cc of concentrated sulfuric acid was added dropwise to the solution while stirring while keeping the temperature at 20°C. After 2 hours, the crystals were collected, washed with a small amount of toluene, and then dried in vacuum.

Crystal yield 0.728g Melting point 99.5-118℃ Elemental analysis amount C(%) H(%) N(%) 44.9 4.7 10.2 Elemental analysis amount S(%) Cl(%) 8.2 9.0 Example 5 2,4-dichlor compound E/Z form (purity 96.8%)
E/Z=43.0/57.0) 8.11g was dissolved in 20g of monochlorobenzene, and 2.45g of concentrated sulfuric acid was added dropwise at 30°C.
Then Z obtained in Example 1 and Example 3, respectively
Approximately 1 mg each of the sulfate salts of the E-isomer and the E-isomer were added. After stirring and keeping at 30°C for 5 hours, the crystals were collected, washed with 10 cc of monochlorobenzene, and then dried in vacuum.

Crystal yield: 7.60 g Melting point: 117-185.5°C Next, 4 c.c. of a 10% aqueous sodium bicarbonate solution, 20 c.c. of toluene, and 20 c.c. of water were added to 1 g of this crystal, and at room temperature (20-25°C), After stirring until the crystals disappeared, the aqueous layer was separated, and the oil layer was washed twice with water and concentrated. The obtained crystals were 0.76 g (purity 99.7%, E/Z=
60.8/39.2).

Example 6 E/Z form of 4-chlor form (purity 92.4%, E/Z form)
=43.3/57.6) 7.84g was dissolved in 40g of toluene,
2.45 g of concentrated sulfuric acid was added dropwise. Then, about 1 mg of the Z-form and E-form sulfates obtained in Example 2 and Example 4, respectively, were added, and the mixture was stirred at 20° C. for 5 hours and then filtered. After washing twice with 10 c.c. of toluene, it was vacuum dried.

Crystal yield 9.06g Melting point 60-85℃ Elemental analysis amount C(%) H(%) N(%) 47.4 4.8 10.1 Elemental analysis amount S(%) Cl(%) 7.5 9.5 Next, 1g of this crystal was added to DMF2c.c After adding 20 c.c. of toluene and 20 c.c. of water, the mixture was thoroughly mixed and the aqueous layer was separated. The oil layer was further washed with water twice and concentrated to obtain the E/Z form (purity 93.7%, E/Z=41.9/
58.1) 0.73g was obtained.

Example 7 The same procedure as in Example 5 was repeated except that 2.45 g of 50% sulfuric acid was used instead of concentrated sulfuric acid and seed crystals were not inoculated.

Crystal 3.35g, moisture 8.4% Melting point 158-165℃ Elemental analysis amount C (%) H (%) N (%) 35.6 4.4 8.3 Element analysis amount S (%) Cl (%) 9.2 16.2 In addition, 1 g of this crystal The E body obtained by decomposing is 0.62
g (E/Z=100.0/0.0).

Example 8 E/Z of 2,4-dichlor compound used in Example 5
8.11 g of the compound was dissolved in 20 g of monochlorobenzene.
After keeping the temperature at 30℃ and dropping 1.22g of concentrated sulfuric acid,
The mixture was stirred at the same temperature for 5 hours and filtered. The crystals were washed with 20 c.c. of monochlorobenzene and then dried in vacuum.
The yield was 4.29 g (melting point 204-205.5°C).

When 5 c.c. of toluene and 10 c.c. of water were added to 2 g of this sulfate and stirred at 40°C for 30 minutes, the crystals almost disappeared. After stirring for another 30 minutes, the aqueous layer was separated and 10 c.c. of water was added.
After washing twice with cc, the oil layer was concentrated. 1.481
The E form (E/Z=98.5/1.5) of g was obtained.

Reference example 1 Crude 2,4-dichlor compound (purity 84.4%, E/Z
= 30.6/69.4) 2g (5.2 mmol as pure content) was dissolved in 5g of monochlorobenzene, and concentrated sulfuric acid was added.
0.279 cc (5.1 mmol) was added dropwise at 30°C, and then about 1 mg of the Z-form sulfate of Example 1 was added. then 30
The mixture was stirred at ℃ for 4 hours, and the precipitated crystals were collected, and the crystals were washed with a small amount of monochlorobenzene. 10 c.c. of water and 10 c.c. of toluene were added to the crystals, and after stirring at 40°C for 1 hour, the aqueous layer was separated, and the oil layer was further washed twice with water and then concentrated. Purity 95.7%, E/Z=
1.48 g (4.4 mmol as pure content) of 2,4-dichlor compound of 33.5/66.5 was obtained.

Claims (1)

[Claims] 1 General formula () [In the formula, X represents a halogen atom, and n represents 1 or 2. ] A sulfate of a triazolyl styryl ketone derivative represented by 2 The triazolyl styryl ketone derivative represented by the above general formula () is 1-(2,4-dichlorophenyl)-2-(1,2,4-triazole-1
-yl)-4,4-dimethyl-1-pentene-3
The sulfate according to claim 1, which is -one. 3 The triazolyl styryl ketone derivative represented by the above general formula () is 1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1 -penten-3-one. 4. The sulfate according to claim 1, 2 or 3, wherein the triazolyl styryl ketone derivative represented by the above general formula () is in the E form. 5. The sulfate according to claim 1, 2, or 3, wherein the triazolyl styryl ketone derivative represented by the general formula () is a Z-form.