JPH04257558A - Production of 4,4'-thiobisbenzenethiol - Google Patents

Abstract

PURPOSE:To provide a method for industrially efficiently producing highly pure 4,4'-thiobisbenzenethiol from diphenyl sulfone in a high yield. CONSTITUTION:In a method for producing 4,4'-thiobisbenzene sulfonyl chloride by sulfonating diphenyl sulfone, chlorinating the produced 4,4'-thiobisbenzene sulfonic acid and subsequently reducing the resultant 4,4'-thiobisbenzene sulfonyl chloride with zinc and/or tin and a mineral acid, the reduction reaction is performed in the presence of lead and/or a lead compound, and all steps are performed in the same solvent without isolating the 4,4'-thiobisbenzene sulfonic acid and the 4,4'-thiobisbenzene sulfonic chloride as the intermediates.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing 4,4'-thiobisbenzenethiol, which is a useful compound having a wide range of uses as an intermediate for industrial chemicals, dyes, and as a raw material for polymeric materials.

0002

[Prior Art and Problems to be Solved by the Invention] Conventionally, as a method for producing 4,4'-thiobisbenzenethiol using diphenyl sulfide as a raw material, the reaction formula is as follows:

[
Diphenylsulfide (I) was sulfonated according to the formula (1).
JP-A-51-15029), the obtained disulfonic acid (
chlorination of II) to give the corresponding sulfonyl chloride (II
I) (Japanese Patent Publication No. 1-28742), which is used to produce (1) zinc (USSR Patent No. 499261), (2) phosphorus (Swiss Patent No. 483407), and (3) tin (J.
Chem. Soc. 33, 812-814 (19
56)) etc. are known.

[0003] However, if these methods are carried out individually, there may be losses when isolating the disulfonic acid (II) or disulfonyl chloride (III), disulfonyl chloride (III) is easily hydrolyzed, etc. For some reason, the yield and conversion rate are low, and it has drawbacks such as the inability to obtain a highly pure product. In view of this situation, the present inventors have made efforts to improve the shortcomings of the conventional methods and to develop a method for industrially producing 4,4'-thiobisbenzenethiol with high efficiency, high yield, and high purity. As a result of repeated efforts, the following findings were obtained. diphenyl sulfide (
During the sulfonation of I), it is extremely difficult to isolate the sulfonic acid (II) with good purity because it is highly hygroscopic. Upon chlorination of 4,4'-thiobisbenzenesulfonic acid (II), (1) 4,4'-thiobisbenzenesulfonyl chloride (III) produced is likely to undergo a hydrolysis reaction with water. (2) The sulfonyl chloride (III) by filtration etc.
When isolating it, it has poor storage stability and is highly irritating, making it unsuitable for industrial use from a safety standpoint.

In addition, when reducing 4,4'-thiobisbenzenesulfonyl chloride (III), (1) trace amounts of lead and/or lead compounds or bismuth and/or When a bismuth compound is present, the amount of reducing agent required is surprisingly almost the same whether isolated and purified 4,4'-thiobisbenzenesulfonyl chloride (III) is used or not. , there is no variation between reactions. (2) Even when isolated and purified, when reducing with zinc in the presence of mineral acids, if trace amounts of lead and/or lead compounds or bismuth and/or bismuth compounds are not present, the amount of zinc required to complete the reaction will be reduced. It varies widely. For example, it depends greatly on the scale of the reaction, stirring speed, zinc addition rate, temperature, zinc particle size, etc., and when using nearly twice as much zinc, it is necessary to remove the water layer and re-add concentrated hydrochloric acid.
Production on an industrial scale was difficult. (3) If the same solvent is used for sulfonation, chlorination, and reduction reactions, the reactions can be carried out in one pot. The present invention was completed based on this knowledge.

[0005]

[Means for solving the problem] Diphenylsulfide is sulfonated to give 4,4'-thiobisbenzenesulfonic acid, and then chlorinated to give 4,4'-thiobisbenzenesulfonyl chloride, which is then treated with zinc and mineral acid. Return 4,4
A method for producing 4,4'-thiobisbenzenethiol, characterized in that the reduction reaction is carried out by adding lead and/or a lead compound or bismuth and/or a bismuth compound. ,and

[0006] Diphenylsulfide is sulfonated to produce 4
, 4'-thiobisbenzenesulfonic acid, followed by chlorination to form 4,4'-thiobisbenzenesulfonyl chloride, and reduction with zinc and mineral acid to obtain 4,4'-thiobisbenzenethiol. , the reduction reaction is carried out by adding lead and/or a lead compound or bismuth and/or a bismuth compound, and the intermediate 4,4'-
Provided is a method for producing 4,4'-thiobisbenzenethiol, characterized in that the reaction is carried out in one pot without isolating thiobisbenzenesulfonic acid and 4,4'-thiobisbenzenesulfonyl chloride. It is something.

According to the method of the present invention, raw material diphenyl sulfide (I) is added to a solvent, and at a predetermined temperature, a sulfonating agent, then a chlorinating agent, a mineral acid for reduction reaction, and finally zinc, lead and / or lead compounds or zinc and bismuth and/or bismuth compounds.
The desired product can be obtained by a simple method of sequentially adding ingredients into a pot. Examples of the solvent used in the sulfonation reaction include ethylene dichloride, chloroform, tetrachloroethylene, and carbon tetrachloride. Particularly good results are obtained when ethylene dichloride and carbon tetrachloride are used. The amount used is in the range of 10 to 20 parts by weight per 1 part by weight of diphenyl sulfide, and preferably,
It is 13 to 17 parts by weight. If the amount is less than 10 parts by weight, 4,4'-thiobisbenzenesulfonic acid (II
), the viscosity of the reaction solution increases and stirring becomes impossible.
Further, if the amount is more than 20 parts by weight, the volumetric efficiency decreases, which is not industrially advantageous.

Examples of the sulfonating agent used include chlorosulfonic acid, sulfuric anhydride, fuming sulfuric acid, and sulfuric acid, with chlorosulfonic acid and sulfuric anhydride being particularly preferred. The amount used is 2.0 to 3.0% relative to diphenyl sulfide.
0 times the mole, preferably 2.0 to 2.2 times the mole. In the subsequent chlorination reaction, chlorinating agents such as chlorosulfonic acid, thionyl chloride, phosphorus chloride, and phosphorus oxychloride are used. The amount of the chlorinating agent used is 2.0 to 3.0 times the mole, preferably 2.0 to 2.3 times the mole of the charged diphenyl sulfide. Moreover, when an amide represented by dimethylformamide is added in a mole of 0.5 to 1.2 times the chlorinating agent during the chlorination reaction, a chlorinated product can be obtained in high yield.

[0009] Solvents used during the reduction reaction include:
Similar to sulfonation and chlorination reactions, halogenated hydrocarbons such as ethylene dichloride, chloroform, tetrachloroethylene, carbon tetrachloride, and methylene chloride, monochlorobenzene, dichlorobenzene, and trichlorobenzene are used. In particular, when sulfonation, chlorination, and reduction are performed in a one-pot reaction, it is preferable to use the same solvent in terms of operability and economy, and good results are obtained when ethylene dichloride and carbon tetrachloride are used. is obtained. For the reduction reaction,
Although zinc is used, good results are obtained if the reaction is carried out in the presence of trace amounts of lead and/or lead compounds or bismuth and/or bismuth compounds. The amount of zinc used is 6 to 13 mol per 1 mol of 4,4'-thiobisbenzenesulfonyl chloride (III) produced. If it is less than 6 moles, the reduction reaction will not be completed,
Not only is a yellow colored 4,4'-thiobisbenzenethiol (IV) of poor quality obtained, but the yield is also reduced. On the other hand, if more than 13 moles are used, no effect commensurate with the addition will be seen, and the volumetric efficiency will decrease, which is not preferable.

As the lead or lead compound, metal lead, lead salts such as lead chloride, lead bromide, lead nitrate, lead sulfate, and lead acetate, and lead oxide are used. As the bismuth or bismuth compound, metal bismuth, bismuth chloride, bismuth bromide, etc. are used. The addition ratio of lead and/or lead compounds to zinc is 200 to 10,000 ppm, preferably 500 to 5,000 ppm, more preferably 1,000 to 1,000 ppm.
It is 3000 ppm. The amount of bismuth and/or bismuth compound added to zinc is 200 to 1
0000 ppm. If the amount is less than 200 ppm, no effect will be seen, and if it is more than 10,000 ppm, no commensurate effect will be seen. Note that it is also within the scope of the present invention to prepare zinc containing these additives within the above numerical range and to reduce using such zinc. Examples of the mineral acid used include hydrochloric acid and sulfuric acid, but hydrochloric acid is preferably used because of its high efficiency in reduction reaction, and the amount used is 1.8 to 1.8 to
It is 2.5 times the mole. If the amount is less than 1.8 times the mole, not only will the reduction reaction be slow, but the metal will not be consumed and will remain in the system. In addition, using more than 2.5 times the mole is not advantageous because not only the corresponding effect cannot be obtained, but also the amount of mineral acid used increases, resulting in a large amount of waste liquid containing metal salts, which becomes difficult to treat. .

[0011]

[Examples] The present invention will be specifically explained below with reference to Examples. In Examples and Comparative Examples, the end point of zinc reduction was determined by sampling the organic layer and determining the color of crystals precipitated at the time of concentration. If the reduction is insufficient, the color turns yellow, and if the reduction is complete, the color is white, so the point at which white crystals precipitated was taken as the end point of the reduction reaction.

Example 1 186.3 g (1.0 mol) of diphenyl sulfide and 2800 g of ethylene dichloride were kept at a temperature of 10° C., and 233.1 g (2.0 mol) of chlorosulfonic acid was added dropwise over 2 hours. The temperature was raised to 20°C and aged for 1 hour. After dropping 146.2 g (2.0 mol) of dimethylformamide at 20°C or lower, the temperature was raised, the reaction solution was kept at 76-80°C, and 238.0 g (2.0 mol) of thionyl chloride was added over 4 hours. dripped. After aging at the same temperature for 2 hours, nitrogen gas was blown in for 3 hours to drive out hydrochloric acid gas and sulfur dioxide gas. When the reaction solution was quantified by liquid chromatography, the yield of 4,4'-thiobisbenzenesulfonyl chloride relative to diphenyl sulfide was 97.8%.
Met.

Vacuum distillation was carried out at 40 to 50°C, and 2400 g of ethylene dichloride was distilled off. Cool to 10°C, filter, and remove 4,4'-thiobisbenzenesulfonyl chloride 23.
7.6 g (0.62 mol) was obtained as the first crystal. The filtrate was further concentrated to obtain 60.7 g (0.16 mol) of second crystals. The yield of 4,4'-thiobisbenzenesulfonyl chloride based on diphenyl sulfide for the first and second crystals was 78%. 2200 g of ethylene dichloride was added to 298.0 g (0.78 mol) of the first and second crystals combined, and then 1560 g of concentrated hydrochloric acid was added at 10°C.
g (15.0 mol) was added. 0.55 g of lead and 546.0 g of zinc were added while increasing the reaction temperature from 10°C to 60°C.
g (8.35 mol) was gradually added over 2 hours, and 60
Aged for 1 hour at ℃. (10.7 times the mole of zinc was used relative to 4,4'-thiobisbenzenesulfonyl chloride.) The aqueous layer was separated and removed, the organic layer was washed with 400 g of 5% hydrochloric acid, and then concentrated under reduced pressure. , filtration dry purity 98.9%
165.2 g of 4,4'-thiobisbenzenethiol (
0.66 mol) was obtained. The obtained yield for 4,4'-thiobisbenzenesulfonyl chloride was 84.5%, and the reduction yield was 96.1% when 4,4'-thiobisbenzenethiol contained in the filtrate was included.

Example 2 Example 1 was repeated, except that instead of adding 0.55 g of lead to the zinc, 0.75 g of bismuth chloride was added before adding the zinc. The amount of zinc used is 540.8g (8.27
The amount was 10.6 times that of 4,4'-thiobisbenzenesulfonyl chloride. Purity 99.0%
167.1 g of 4,4'-thiobisbenzenethiol (
0.67 mol) was obtained. The obtained yield for 4,4'-thiobisbenzenesulfonyl chloride was 85.9%, and the reduction yield was 95.9% when 4,4'-thiobisbenzenethiol contained in the filtrate was included.

Example 3 186.3 g (1.0 mol) of diphenyl sulfide and 2800 g of ethylene dichloride were kept at a temperature of 10° C., and 233.1 g (2.0 mol) of chlorosulfonic acid was added dropwise over 2 hours. The temperature was raised to 20°C and aged for 1 hour. After dropping 146.2 g (2.0 mol) of dimethylformamide at 20°C or lower, the temperature was raised, the reaction solution was kept at 78-80°C, and 238.0 g (2.0 mol) of thionyl chloride was added over 4 hours. dripped. After aging at the same temperature for 2 hours, nitrogen gas was blown in for 3 hours to drive out hydrochloric acid gas and sulfur dioxide gas. When the reaction solution was quantified by liquid chromatography, the yield of 4,4'-thiobisbenzenesulfonyl chloride based on diphenyl sulfide was 97.7%.
Met. 2000 g (19.2 mol) of concentrated hydrochloric acid was added to this solution, and 0.70 g of lead and 686.4 g (10.5 mol) of zinc were gradually added to the solution for 2 hours while raising the reaction temperature from 10°C to 60°C. The mixture was added over a period of time and aged at 60°C for 1 hour. (Zinc was used in an amount of 10.7 times the mole of 4,4'-thiobisbenzenesulfonyl chloride.) After carrying out the above reaction in one pot, the aqueous layer was separated and removed.
The organic layer was washed with 500 g of % hydrochloric acid, concentrated under reduced pressure, and filtered and dried to obtain 208.0 g (0.83 mol) of 4,4'-thiobisbenzenethiol with a purity of 98.9%. The obtained yield for 4,4'-thiobisbenzenesulfonyl chloride was 85.0%, and the 4,4' contained in the filtrate was
-If thiobisbenzenethiol is included, the reduction yield is 95
．． It was 8%.

Example 4 The same procedure as in Example 1 was carried out except that instead of 0.55 g of lead, 1.0 g of lead chloride was added in advance before adding zinc. The amount of zinc used was 542.7g (8.30 mol), 4.4
10 for '-thiobisbenzenesulfonyl chloride
．． Six times the molar amount of zinc was used. As a result, purity 99.0
% 4,4'-thiobisbenzenethiol 166.4g
(0.66 mol) was obtained. Obtained yield for 4,4'-thiobisbenzenesulfonyl chloride was 84.6%
When 4,4'-thiobisbenzenethiol contained in the filtrate was included, the reduction yield was 96.0%.

Comparative Example Except for using zinc which does not substantially contain lead or bismuth,
The same procedure as in Example 1 was carried out. Sampling was performed when the same amount of zinc as in Example 1 was added, but a yellow solid was obtained, so 500 g of concentrated hydrochloric acid was added and zinc was gradually added. An additional 193.0 g of zinc was added until sampling yielded a white solid. The total amount of zinc used is 739
．． As a result of using 14.5 times the mole of zinc to 4,4'-thiobisbenzenesulfonyl chloride, 4,4'-thiobisbenzenethiol with a purity of 98.7% was obtained. 161.7 g (0.65 mol) was obtained. The obtained yield for 4,4'-thiobisbenzenesulfonyl chloride was 82.8%, and the 4,4'-thiobisbenzenesulfonyl chloride contained in the filtrate was
, 4'-thiobisbenzenethiol was included, the reduction yield was 93.3%. Note that when using zinc that does not substantially contain lead or bismuth, the amount of zinc required to complete the reduction reaction varies greatly from experiment to experiment.
1 for 4'-thiobisbenzenesulfonyl chloride
It was 4.5 times the mole, and in the most cases it was 27.2 times the mole.

Example 5 Instead of using lead and zinc in Example 1, 1 lead was used.
The reaction was carried out in the same manner as in Example 1 except that the reduction was performed using zinc containing 000 ppm. The amount of zinc used is 541
．． Zinc was used in an amount of 3 g (8.28 moles), which was 10.6 times the mole of 4,4'-thiobisbenzenesulfonyl chloride. As a result, 163.7 g (0.65 mol) of 4,4'-thiobisbenzenethiol with a purity of 99.2% was obtained. The obtained yield for 4,4'-thiobisbenzenesulfonyl chloride was 83.3%, and the 4,4'-thiobisbenzenesulfonyl chloride contained in the filtrate was
, 4'-thiobisbenzenethiol was included, the reduction yield was 96.0%.

[0019]

[Effect of the invention] Using diphenyl sulfide as a raw material, 4
, 4,4'- via 4'-thiobisbenzenesulfonic acid
When synthesizing thiobisbenzenesulfonyl chloride and reducing it with zinc in the presence of a mineral acid to obtain 4,4'-thiobisbenzenethiol, trace amounts of lead and/or lead compounds or bismuth and/or bismuth compounds were added. When reduction is performed by adding zinc, the reduction reaction proceeds with almost the same amount of zinc as when the isolated and purified sulfonyl chloride is used as the reduction raw material. It is also possible to prevent variations in the amount of zinc used for each reaction. Furthermore, by using the same solvent for each reaction, the desired product can be easily obtained in one pot without isolating the intermediate. Therefore, compared to conventional methods for isolating intermediates, not only the number of filtration times is reduced, but also a product with a higher yield and the same quality can be obtained.

Claims (4)

[Claims] Claim 1: Diphenylsulfide is sulfonated to give 4,4'-thiobisbenzenesulfonic acid, then chlorinated to give 4,4'-thiobisbenzenesulfonyl chloride, and reduced with zinc and mineral acid to give 4,4'-thiobisbenzenesulfonyl chloride. , 4'-thiobisbenzenethiol, characterized in that the reduction reaction is carried out by adding lead and/or a lead compound or bismuth and/or a bismuth compound.
Method for producing 4'-thiobisbenzenethiol. 2. Diphenylsulfide is sulfonated to give 4,4'-thiobisbenzenesulfonic acid, then chlorinated to give 4,4'-thiobisbenzenesulfonyl chloride, and reduced with zinc and mineral acid to give 4,4'-thiobisbenzenesulfonyl chloride. , 4'-thiobisbenzenethiol, the reduction reaction is carried out by adding lead and/or a lead compound or bismuth and/or a bismuth compound, and the intermediate 4,4
'-thiobisbenzenesulfonic acid and 4,4'-thiobisbenzenesulfonyl chloride without isolating
4,4'- characterized in that the reaction is carried out in one pot.
Method for producing thiobisbenzenethiol. [Claim 3] Claim 1, wherein the amount of lead and/or lead compounds added is 200 to 10,000 ppm relative to zinc.
Or the method according to claim 2. 4. The method according to claim 1, wherein the amount of bismuth and/or bismuth compound added is 200 to 10,000 ppm based on zinc.