JPH08333330A - Method for producing bis (4-chlorophenyl) sulfide - Google Patents

Abstract

PURPOSE: To directly produce bls(4-chlorophenyl) sulfide useful as an intermediate, etc., for polysulfones, etc., which are engineering plastics from monochlorobenzene and sulfur chlorides. CONSTITUTION: Monochlorobenzene is reacted with sulfur chlorides (sulfur chloride, etc.) by using the monochlorobenzene as a solvent and an iron-based catalyst (iron powder, etc.) as a catalyst to thereby afford bls(4-chlorophenyl) sulfide. Furthermore, the reaction is carried out by using the iron-based catalyst in a molar amount of 0.00001-0.1 based on the monochlorobenzene used and the sulfur chlorides in a molar amount of 0.0001-0.5 based on the monochlorobenzene used at 0-150 deg.C reactional temperature.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for directly producing bis (4-chlorophenyl) sulfide from monochlorobenzene, more specifically by reacting sulfur chlorides with monochlorobenzene under a monochlorobenzene solvent and an iron catalyst. The present invention relates to a method for producing bis (4-chlorophenyl) sulfide.

[0002]

BACKGROUND OF THE INVENTION Bis (4-chlorophenyl) sulfide is a compound useful as an intermediate for engineering plastics such as polysulfone and polyethersulfone, and as an intermediate for medicines and agricultural chemicals. Examples of the method include reducing bis (4-chlorophenyl) sulfoxide (EP-68371,
Synth.Commum, 17 , 1403 (1987)), a method of chlorinating diphenyl sulfide (JP-A-55-17362, JP-A-1-
No. 106858) is known. However, bis (4-chlorophenyl) was obtained directly from monochlorobenzene.
No method is known for producing sulfides.

On the other hand, as a method for directly producing an aromatic sulfide corresponding to an aromatic compound having an electron-donating group such as anisole and sulfur chlorides, ether is used as a solvent and iron-based, tin-based or zinc-based catalysts are used. A method using such a catalyst has been proposed (Japanese Patent Publication No. 45-17676). It is also known that 4-chlorophenylsulfenyl chloride is produced by the action of sulfur chlorides on monochlorobenzene in a methylene chloride solvent and an iron-based catalyst (Proceedings of the 3rd Symposium on Organic Sulfur Chemistry, page 47 ( 1969)). However, in the former method, the desired bis (4-chlorophenyl) sulfide was not obtained even when monochlorobenzene was used instead of anisole, and the latter method was also used. Very little 4-chlorophenyl) sulfide was obtained.

[0004]

Under these circumstances, the inventors of the present invention have conducted diligent studies in order to directly produce bis (4-chlorophenyl) sulfide from monochlorobenzene, and as a result, use monochlorobenzene as a solvent. The present invention has been completed by finding that the desired bis (4-chlorophenyl) sulfide can be produced in a good yield if it is carried out under a specific condition that an iron-based catalyst is used as the catalyst.

That is, the present invention is characterized in that sulfur chlorides are allowed to act on monochlorobenzene in the presence of a monochlorobenzene solvent and an iron-based catalyst.
A method for producing a sulfide is provided.

The present invention will be described in detail below. The present invention is characterized by using monochlorobenzene as a solvent and using an iron-based catalyst as a catalyst.
Examples of the iron-based catalyst include iron, ferric chloride, ferrous chloride, ferric bromide, ferrous bromide, and mixtures of two or more thereof. Iron, ferric chloride, a mixture thereof and the like are preferably used. Here, when using iron, 10
Powders of about 400 mesh are usually used. The iron-based catalyst is usually 0.0000 with respect to the monochlorobenzene used.
It is used in a molar amount of 1 to 0.1, preferably 0.001 to 0.01. The amount used for sulfur chlorides is usually 0.001 to 0.
3 molar times.

Examples of sulfur chlorides include sulfur chloride, sulfur dichloride and mixtures thereof. Sulfur chlorides are
Normally 0.0001 to 0 for the monochlorobenzene used.
It is used 5 times by mol, preferably 0.001 to 0.1 times by mol.
The reaction is usually performed at about 0 to 150 ° C, preferably about 10 to 80 ° C.

Thus, the desired bis (4-chlorophenyl) sulfide is produced, but it can be separated and purified from the reaction mixture by a usual means such as extraction, recrystallization and various chromatographic separation means.

[0009]

EFFECTS OF THE INVENTION According to the present invention, bis (4-chlorophenyl) is obtained directly from monochlorobenzene and sulfur chlorides by carrying out under the specific conditions that monochlorobenzene is used as a solvent and an iron-based catalyst is used as a catalyst. )
Sulfides can be produced.

[0010]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 17 mg (0.3 mmol) of iron powder in 5 ml of monochlorobenzene at 25 ° C.
After adding, 386mg of sulfur dichloride (Purity 80%, made by Aldrich)
(3 mmol) was added dropwise, and the mixture was stirred at the same temperature for 12 hours. Then, water and ethyl acetate were added for extraction, the organic layer was dried over anhydrous magnesium sulfate, the low boiling fraction was distilled off, and the residue was purified by silica gel thin layer chromatography (developing solution: hexane) to give bis (4-chlorophenyl). ) Sulfide 113 mg
I got

Example 2 In Example 1, 405 m of sulfur chloride was used instead of sulfur dichloride.
The reaction was carried out according to Example 1 except that g (3 mmol) was used. Then, water and ethyl acetate were added for extraction, the organic layer was dried over anhydrous magnesium sulfate, the low boiling fraction was distilled off, and the residue was analyzed by gas chromatography. The amount of bis (4-chlorophenyl) sulfide produced was 89 mg.

Example 3 In Example 1, 49 mg (0.3%) of ferric chloride was used instead of iron powder.
mmol), and then sulfur dichloride (purity 80%) 386 mg (3 mmo
When l) was added dropwise, the reaction was violent after 1-2 minutes, and monochlorobenzene was refluxed. After 15 minutes, water and ethyl acetate were added, and post-treatment and analysis were carried out in accordance with Example 2. Screw (4
The amount of -chlorophenyl) sulfide produced was 58 mg.

Example 4 In Example 1, 49 mg (0.3%) of ferric chloride was used instead of iron powder.
After the reaction was carried out in accordance with Example 1 except that 405 mg (3 mmol) of sulfur chloride was added dropwise, the post-treatment and analysis were carried out according to Example 2. The amount of bis (4-chlorophenyl) sulfide produced was 134 mg.

Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that a mixture of 3 ml of methylene chloride and 675 mg (6 mmol) of monochlorobenzene was used in place of 5 ml of monochlorobenzene, and the mixture was stirred for 13 hours. The post-treatment and analysis were carried out in accordance with Example 2. The amount of bis (4-chlorophenyl) sulfide produced was 18 mg.

Comparative Example 2 In Example 1, instead of 5 ml of monochlorobenzene, 3 ml of diethyl ether and 675 mg of monochlorobenzene (6 mmo)
Using the mixture consisting of l), the reaction was carried out according to Example 1 except that the mixture was stirred for 13 hours, and post-treated and analyzed according to Example 2. No formation of bis (4-chlorophenyl) sulfide was observed.

Comparative Example 3 In Example 1, 41 mg (0.3 mm of zinc chloride was used instead of iron powder.
The reaction was carried out in accordance with Example 1 except that the mixture was stirred for 13 hours, and post-treatment and analysis were carried out in accordance with Example 2.
No formation of bis (4-chlorophenyl) sulfide was observed.

Comparative Example 4 In Example 1, instead of iron powder, anhydrous stannous chloride 57 was used.
Using mg (0.3 mmol), the reaction was carried out according to Example 1 except that the mixture was stirred for 13 hours, and post-treated and analyzed according to Example 2. No formation of bis (4-chlorophenyl) sulfide was observed.

Claims (3)

[Claims] 1. A method for producing bis (4-chlorophenyl) sulfide, which comprises reacting monochlorobenzene with sulfur chlorides in the presence of a monochlorobenzene solvent and an iron-based catalyst. 2. The method according to claim 1, wherein at least one selected from iron and ferric chloride is used as the iron-based catalyst. 3. The method according to claim 1, wherein at least one selected from sulfur chloride and sulfur dichloride is used as the sulfur chlorides.