JP2807029B2 - Method for producing bis [(4-hydroxy-3-phenyl) phenyl] sulfide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to bis ((4-hydroxy-) which is a bisphenol useful as a raw material for polycarbonates, polyesters, epoxy resins, phenol resins, various other polymer materials, and agricultural and pharmaceutical materials. The present invention relates to 3-phenyl) phenyl) sulfide and a method for producing the same.

[Prior Art] This bis ((4-hydroxy-3-phenyl) phenyl) sulfide is disclosed in Journal of the American Pharmaceutical Association.
21 557-69 (1932).

According to this document, an oily bis ((4-hydroxy-3-phenyl) phenyl) sulfide was obtained by reacting sulfur dichloride of o-phenylphenol at a low temperature with carbon disulfide as a solvent. ing.

Further, as a result of additional tests by the present inventors, similar oily substances were obtained even when other general-purpose solvents such as benzene, toluene, and 1,2-dichloroethane were used.

However, the oily substance was analyzed by high performance liquid chromatography and found to be a mixture containing many components.

From this, the oily substance is different from bis ((4-hydroxy-3-phenyl) phenyl) sulfide, and bis ((4-hydroxy-3-phenyl) phenyl) sulfide has not been isolated yet. .

Therefore, although a polymer utilizing this compound is not known, properties predicted from its structure are considered to be extremely useful.

[Problems to be solved by the invention]

The present invention has been made in view of the above problems, and provides a method for selectively producing bis ((4-hydroxy-3-phenyl) phenyl) sulfide, which is a promising diphenol as a raw material for various polymers. is there.

[Means for solving the problem]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention.

The present invention relates to a method for reacting o-phenylphenol with sulfur dichloride, wherein the compound represented by the general formula (I) (Wherein, R _{1 to} R ₃ represent a hydrogen atom, a halogen atom,
8 represents a linear or branched alkyl group, aryl group or aralkyl group. This is a method for selectively producing bis ((4-hydroxy-3-phenyl) phenyl) sulfide by the presence of a nitrile represented by the following formula:

In the method of the present invention, although the catalytic action of the nitriles is not clear, since o-phenylphenol has almost no regioselectivity in the reaction to the hydroxyl group, when sulfur dichloride is reacted under ordinary conditions, Although a large amount of an isomer mixture or condensate was produced and a composition that could isolate the target product was not obtained, surprisingly, when nitriles were present in the reaction system, only the para position was selectively obtained. The present inventors have found that they combine, and completed the present invention.

Examples of the nitriles used in the present invention include acetoniloryl, chloroacetonitrile, dichloroacetonitrile, propionitrile, 2,2-dichloropropionitrile, 2,2-dimethylpropionitrile,
Butyronitrile, 4-chlorobutyronitrile, isobutyronitrile, valeronitrile, benzonitrile, α-tolunitrile, o-tolylacetonitrile, m-tolylacetonitrile, p-tolylacetonitrile, and the like are used. Any amount that also serves as a solvent can be used from about 10 mol% to o-phenylphenol, but preferably about 50 mol% to 500 mol%.

In the reaction of the present invention, an acid catalyst may be used in combination. As the acid catalyst, mineral acids such as hydrochloric acid and phosphoric acid and Lewis acids such as aluminum chloride, zinc chloride and iron chloride are used. The amount is about 0.01 to 10% (% by weight), preferably about 0.01 to 1% (% by weight).

The bis ((4-hydroxy-3-phenyl) phenyl) sulfide of the present invention suppresses the formation of isomers and other by-products by reacting o-phenylphenol with sulfur dichloride in the presence of nitriles. Can be generated efficiently, but the o
The amount of phenylphenol is about 2 to 5 moles, preferably about 2.0 to 2.5 moles per mole of sulfur dichloride.

As a form of the reaction, a method in which o-phenylphenol, an acid catalyst, and nitriles are charged into a reaction vessel, and sulfur dichloride is dropped into this mixture is preferable, but is not particularly limited.

At this time, the amount of the nitrile used is not limited as long as it can be used as a solvent and can be sufficiently stirred. However, when stirring is difficult due to the amount of the catalyst, a solvent which does not participate in the reaction may be used.

As this solvent, for example, benzene, toluene, 1,2
It does not participate in the reaction of -dichloroethane, 1,1,1-trichloroethane, hexane, cyclohexane, acetic acid and the like, and its use amount may be any amount.

The reaction temperature is not higher than 20 ° C, preferably in the range of 5 to -10 ° C.

The reaction of the present invention is an exothermic reaction, and the dropping time of sulfur dichloride is desirably a rate that can maintain the reaction temperature. Usually 1
The range is ~ 10 hours.

After the acid catalyst and by-product hydrochloric acid are sufficiently removed from the reaction solution thus obtained by washing with water or the like, bis ((4-hydroxy-3) is obtained by an arbitrary method such as concentration, crystallization, recrystallization, or a combination thereof. -Phenyl) phenyl) sulfide can be crystallized and purified.

Next, the present invention will be described in more detail by examples,
The present invention is not limited by this.

〔Example〕

Example 1 In a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel,
343.6 g (2.02 mol) of o-phenylphenol, zinc chloride
Charge 2.3 g (0.5%) and 343.6 g of acetonitrile and cool to −10 ° C. with stirring.

103g of sulfur dichloride (1.0m
ol) and 103 g of acetonitrile were added dropwise.

At this time, the dropping rate was adjusted so that the temperature did not rise due to the heat generated by the reaction, and the dropping was completed in 3 hours.

 The reaction temperature during the dropwise addition was -8 to -10C.

After completion of the dropwise addition, stirring was continued for 1 hour while maintaining the temperature at -10 ° C, and then the reaction was terminated.

At this time, the content of the main component considered to be bis ((4-hydroxy-3-phenyl) phenyl) sulfide with respect to all the reaction products was 85.8% (by high performance liquid chromatography). The reaction solution was charged with 500 ml of toluene, and washed with water until the waste water became neutral.

Next, volatile matter was removed from the organic layer by a rotary evaporator to obtain a yellow oily substance.

This oily material was largely crystallized at room temperature.

The oily substance thus obtained was dissolved by heating in 350 g of toluene, and then gradually cooled to room temperature to obtain 281.2 g of white crystals. Its purity by high performance liquid chromatography was 95.7%.

Further, by performing recrystallization twice with toluene, crystals having a purity of 98.8% were obtained (total yield: 65.6%).

 The other analysis results are shown below.

(1) Melting point 122-123 ° C. (2) Elemental analysis C H S Calcd (%) 77.84 4.86 8.65 measurements (%) 77.88 4.82 8.82 (3 ) H-NMR ((CD 3) 2 CO: TMS) ppm FIG. 1 shows an NMR absorption spectrum.

(4) IR Fig. 2 shows the infrared absorption spectrum.

From the above results, it was confirmed that the obtained crystal was bis ((4-hydroxy-3-phenyl) phenyl) sulfide.

Example 2 The same operation as in Example 1 was carried out except that the reaction temperature was changed to 0 to 5 ° C.

At this time, the bis ((4-hydroxy-3-phenyl) phenyl) sulfide content was 75.6%.

Example 3 A reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel was placed in a reaction vessel.
-Phenylphenol 34.8 g (0.205 mol), zinc chloride 0.2
2 g (0.5%), 4.1 g (0.1 mol) of acetonitrile, and 34.8 g of toluene were further charged, and 10.3 g of sulfur dichloride (0.
A mixture of 1 mol) and 10.3 g of toluene was added dropwise to carry out the reaction.

 The reaction conditions are the same as in Example 1.

At this time, the bis ((4-hydroxy-3-phenyl) phenyl) sulfide content was 71.3%.

Example 4 A reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel was charged with o.
-Phenylphenol 34.8 g (0.205 mol), zinc chloride 0.2
2g (0.5%) and 7.6g of chloroacetonitrile (0.1mo
l), further charged with 34.8 g of toluene, and sulfur dichloride
A mixture of 10.3 g (0.1 mol) and 10.3 g of toluene was dropped and reacted.

 The reaction conditions are the same as in Example 1.

At this time, the content of bis ((4-hydroxy-3-phenyl) phenyl) sulfide was 72.1%.

〔The invention's effect〕

As described in detail above, bis ((4-hydroxy-3-phenyl) phenyl} useful as a raw material for various polymers is used.
Sulfides could only be isolated by the method of the invention.

The method of the present invention can be selectively reacted in the para position by the presence of nitriles, so that
The desired product can be obtained in high yield.

[Brief description of the drawings]

FIG. 1 is a diagram showing an NMR absorption spectrum of the compound obtained in Example 1, and FIG. 2 is a diagram showing an IR absorption spectrum of the compound.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C07C 323/20 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. An o-phenylphenol and sulfur dichloride,
General formula (I) (Wherein, R _{1 to} R ₃ represent a hydrogen atom, a halogen atom,
8 represents a linear or branched alkyl group, aryl group or aralkyl group. A method for producing bis [(4-hydroxy-3-phenyl) phenyl] sulfide, characterized by reacting in the presence of a nitrile represented by the following formula: