JPS60190756A - Production of 1,7-di(4-hydroxyphenylthio)-3,5-dioxaheptane - Google Patents

Abstract

PURPOSE:4,4-Dihydroxiphenyl sulfilde is reduced and the resultant 4-mercaptolhenol is, without any particular purification proces, subjected to a series of continuous chemical process to form the titled compound of high purity. CONSTITUTION:4.4'-Dihydroxydiphenyl disulflide is reduced by a known method to give a solution of 4-mercaptophenol in an aqueous organic solvent and the solution is brought into contact with an alkaline aqueous solution to effect extraction. The 4-mercaptophenol included in the aqueous solution is heated together with bis(2-haloethoxy)methane at 60-80 deg.C for 1-2hr to give the objective compound. The reaction according to the present invention makes the isolation of the reaction intermediate, 4-mercaptophenol, unnecessary and it possible to avoid oxidation, resulting in no convertion into 4,4'-dihydroxydiphenyl disulfide.

Description

Detailed Description of the Invention [Technical Field] The present invention provides an industrially advantageous method for producing 1,7-di(4-hydroxyphenylthio)-3,5-dioxahebutane by a series of continuous operations. It is related to.

[Prior art]

], 7-di(4-hydroxyphenylthio)-3,5-
Dioxahebutane (hereinafter abbreviated as DHTD) is a new compound proposed by one applicant as an invention in Japanese Patent Application No. 57-216360, and is represented by the following structural formula.

According to the method proposed earlier, DIITD can be obtained by dissolving 4-mercap (hephenol in an alkaline solution and adding the general formula %) (where X is a halogen and chlorine, bromine, etc. It is produced by reacting bis(2-haloethoxy)methane represented by In this case, 4-mercaptophenol used as a raw material can be produced by various methods, but in order to obtain a highly pure product, it is necessary to purify it by a purification process such as distillation.

However, such purified products are easily oxidized in the air and converted to 4,4'-dihydroxydiphenyl disulfide, so there is a problem that they must be sealed in an inert gas such as nitrogen gas. .

〔the purpose〕

The present inventors avoided the above-mentioned oxidation of 4-mercaptophenol, and also purified 4-mercaptophenol into the target D by a series of continuous steps without going through any special purification steps.
As a result of intensive research to develop a method for producing IITD with high purity, the present invention was completed.

〔composition〕

That is, according to the present invention, a water-insoluble organic solvent solution containing 4-mercaptophenol is produced from a reduction product of 4,4'-dihydroxydiphenyl disulfide, and an alkaline aqueous solution is brought into contact with this organic solvent solution to dissolve the organic solvent. After the 4-mercaptophenol contained in the solution is extracted into the alkaline aqueous solution, the 4-mercaptophenol contained in the aqueous solution is extracted.
Provided is a method for producing 1,7-di(4-hydroxyphenylthio)-3,5-dioxahebutane, which comprises reacting mercaptophenol and bis(2-haloethoxy)methane.

When carrying out the method of the present invention, first, 4,4'-dihydroxydiphenyl disulfide is used as a starting material and is subjected to a reduction treatment. In this case, the reduction treatment can be performed by a conventionally known method, for example, using a combination of a metal such as iron, zinc, or tin and a mineral acid such as hydrochloric acid or sulfuric acid. This reduction reaction produces 4-mercaptophenol.

Next, in the case of the present invention, a water-insoluble organic solvent solution containing 4-mercaptophenol is prepared from this reduction reaction product. The water-insoluble organic solvent solution containing 4-mercaptophenol can be prepared by adding a water-insoluble organic solvent to the reduction reaction product and transferring 4-mercaptophenol to this solvent.
It can also be carried out by pre-existing a water-insoluble organic solvent. As the water-insoluble organic solvent, for example, hydrocarbon solvents such as benzene, toluene, and xylene are suitable.

Next, an alkaline aqueous solution is brought into contact with this water-insoluble organic solvent solution of 4-mercaptophenol, and 4-mercaptophenol is extracted and transferred to the alkaline aqueous solution. The alkaline aqueous solution in this case can be obtained by dissolving an alkaline substance such as sodium hydroxide or potassium hydroxide 11 in water. When extracting 4-mercaptophenol, the P)I of the alkaline aqueous solution is approximately 7.6.
It is best to maintain the value at ~9.0. Further, prior to extraction of this alkaline aqueous solution, the water-insoluble organic solvent solution containing 4-mercaptophenol can be decolorized using a decolorizing adsorbent such as activated carbon or activated clay.

Next, 4-mercaptophenol contained in the alkaline aqueous solution and bis(2-haloethoxy)methane are reacted. One way to perform this reaction is to use 4-
A water-soluble organic solvent such as methanol or ethanol is added in advance to an alkaline aqueous solution of mercaptophenol, and then bis(2-haloethoxy)methane is added at room temperature or under heating. In this case, the amount of water-soluble organic solvent added to the alkaline aqueous solution of 4-mercaptophenol is usually 5
The density is preferably 0 to 85% by weight, preferably 75 to 85% by weight. Furthermore, after the addition of bis(2-haloethoxy)methane, the reaction between 4-mercaptophenol and bis(2-haloethoxy)methane is carried out at 60 to 80°C.
Preferably, it is carried out by heating to 60 to 70°C for 1 to 2 hours. After completion of this reaction, the target DHTD crystals are separated and recovered by a conventional method such as a concentration method or a crystallization method.

Another method for reacting 4-mercaptophenol and bis(2-haloethoxy)methane is to carry out the reaction in the presence of a phase transfer catalyst.

In this case, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol may be present if necessary. Phase transfer catalysts are defined as those that have a catalytic effect of solubilizing target nuclides and bases that are insoluble in organic solvents with quaternary onium and crowns, and include amines, quaternary ammonium salts,
Includes phosphonylam salts, crown ethers, etc.
Regarding such phase transfer catalysts, for example, in the literature,
Co-translated by Reyofushi and Yotsuya, “Phase Transfer Catalyst” (Kagaku Doujin, 197
B). Specific examples of such phase transfer catalysts include amines such as tertiary amines such as 1-trimethylamine and triethylamine, and quaternary ammonium salts such as trioctylmethylammonium. chloride, N-laurylpyridinium chloride, triethylbenzylammonium bromide, and the like, and examples of phosphonium salts include tetraphenylphosphonium chloride,
Triphenylmethylphosphonium iodide, tetrabutylphosphonium chloride, etc. are mentioned, and regarding crown ethers, for example, dibenzo-18-crown-6, dicyclohexyl-18-crown-6,18
-Crown-6 etc. can be mentioned.

As a phase transfer catalyst, it is particularly suitable to use a quaternary ammonium salt, and examples of the salt in this case include hydrochloride (chloride), hydrogen sulfate (hydrozine sulfate), etc.
salts of various inorganic and organic acids, such as perchlorates (Baku, Lore 1-), toluenesulfonates, and the like.

The reaction in the presence of the phase transfer catalyst is easy to carry out and can be carried out at a temperature around room temperature, usually from 15 to 40°C. In this case, the reaction is preferably carried out, for example, about 0% per mole of 4-mercaptophenol.
．． 5 mol of bis(2-haloethoxy)methane may be added and mixed, and about 0.1 mol of phase transfer catalyst may be added to this mixture, followed by vigorous stirring at a temperature around room temperature. Through this reaction, a mixture of DIITD, which is the target product, and alkali halide, which is a by-product, precipitates out. After the reaction is complete, enough hot water is added to elute the alkali halide, and the mixture is stirred for a while. Then, the precipitate is filtered and washed to obtain the desired product in the form of a highly pure white powder.

〔effect〕

The method of the present invention has the above-mentioned configuration, and the target DIITD can be obtained through a series of continuous steps using 4,4'-dihydroxydiphenyl disulfide as a starting material,
During this time, there is no need to isolate 4-mercaptophenol, which is a reaction intermediate, so the reaction operation is simple.
In addition, 4-mercaptophenol undergoes oxidation, resulting in 4,4
It is not converted to '-dihydroxydiphenyl disulfide.

Therefore, the method of the present invention is extremely advantageous as an industrial method for producing D HTO.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 4.4'-dihydroxydiphenyl disulfide 50
．． Add 35.4g of zinc powder and 50mQ of toluene to 0g,
Add 10 mQ of water and cool on ice while stirring well.
123 g of 36% hydrochloric acid was added dropwise at 0° C. or below, and a reduction reaction was carried out by a conventional method. After the reaction is completed, the toluene layer is separated and extracted using 25% aqueous sodium hydroxide solution 60g. At this time, the extraction process is performed while adjusting the pH to 7.90. Next, add 200 ethanol to this extract.
m Q was added, and while stirring, 31.2 g of bis(2-chloroethoxy)methane was cooled at room temperature, cooled for 1 time, and then heated under reflux for 3 hours. After the reaction is completed, methanol is recovered by distillation, and then a small amount of water is added to cool it.

The precipitated crystals were collected by filtration and recrystallized with 50% aqueous methanol to obtain the desired crystals of DHTD (mp108-111°).
C) 55.9g was obtained. The yield was 79.3% based on 4.4'-dihydroxy-diphenyl disulfide.

Example 2 4.4'-dihydroxydiphenyl disulfide 50
．． The procedure was carried out in the same manner as in Example 1 using 0 g, pH 8, oO
An extract of an aqueous sodium hydroxide solution was obtained. To this extract, 31.2 g of bis-(2-chloroethoxy)methane was added, and further, 5 g of a 90% aqueous solution of trioctylmethylammonium chloride (tt) was added, and the mixture was reacted with vigorous stirring. After continuing stirring at room temperature to 30°C for 2 hours, the precipitated crystals were collected by filtration and thoroughly washed with 30°C warm water. Furthermore, it is recrystallized with a toluene-ethyl acetate mixed solvent to crystallize the desired DHTD (mpH7.5~
110° C.) 44.7 g was obtained. The yield was 63.4% based on 4.4'-dihydroxydiphenyl disulfide.

Patent Applicant Ricoh Co., Ltd. - Attorney Toshiaki Ikeura Proceedings Amendment September 1980 Z (1st Japan Patent Office Commissioner Manabu Shiga 1, Indication of Case 1982 Patent Application No. 045880 2, Name of the invention 1.7-di(4-hydroxyphenylthio)-3,5-
Process for producing dioxahebutane 3, relationship with the amended case Patent applicant address 1-3-6 Nakamagome, Ota-ku, Tokyo Name (
674) Rico Co., Ltd. - Representative Hama 1) Hiro 4, Agent 〒151 Address 1-58-10-5 Yoyogi, Shibuya-ku, Tokyo Date of amendment order Voluntary 6 Number of inventions increased by amendment 0 7. Column 8, "Detailed Description of the Invention" of the specification to be amended, Contents of the amendment The following amendments will be made in the specification of the application.

(1) Change rpl17.901 on page 9, line 19 to rp
l(Corrected to 8,,90J.

(2) “Ethanol 2” from the last line of page 9 to the first line of page 10
Correct 00m It J to [methanol 200+n Q J.

(3) rpl8.00J on page 10, line 11, rp
I will correct it to l+9.004.

(4) rll, 5gJ on page 10, line 15, rl
, corrected to 9gJ.

(5) r (mpH7,5~llO℃)J on the last line of page 10
Correct it to "r (mp107.5-110℃)".

Claims (1)

[Claims] (1) A water-insoluble organic solvent solution containing 4-mercaptophenol is produced from the reduction product of 4.4'-dihydroxydiphenyl disulfide, and an alkaline aqueous solution is brought into contact with this organic solvent solution to remove the 4-mercaptophenol contained in the organic solvent solution. - 1,7-di(4-hydroxyphenylthio) characterized by extracting mercaptophenol into the alkaline aqueous solution and then reacting 4-mercaptophenol contained in the aqueous solution with bis(2-haloethoxy)methane. )-3,5-dioxahebutane manufacturing method.