KR830001325B1 - Method for preparing bisphenol sulfone derivative - Google Patents

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Method for preparing bisphenol sulfone derivative

The present invention relates to a process for the preparation of bisphenol sulfone derivatives.

In general, oxidation of sulfur compounds is carried out using only hydrogen peroxide as an oxidizing agent in glacial acetic acid solution (peracetic acid oxidation). The following methods and the like have been known for a method of oxidizing bisphenol sulfide or bisphenol sulfoxide to obtain corresponding sulfones. .

(1) Oxidation of sulfide by hydrogen peroxide is usually carried out in glacial acetic acid (peracetic acid oxidation) or in an organic solvent such as acetone.

(2) The oxidation of 2 2'-bisphenol sulfide by hydrogen peroxide in glacial acetic acid in a similar manner to the above to obtain the corresponding 2,2'-bisphenol sulfone derivatives (J. Am. Chem. Soc., 7. 238 (1966).

(3) A known method for oxidizing 4,4'-dikenolsulphides in an acid aqueous solution in the presence of a metal catalyst such as molybdenum, vanadium, titanium, tungsten, or the like to obtain 4,4'-diphenolsulfone, or 4,4'- Diphenolsulfide is adjusted to pH 1 or below, and then heated to reflux in the presence of molybdenum to obtain the final target in 99.7% yield (97.% purity) (US Pat. No. 4,089,904)

(4) In preparing bisphenol sulfone by oxidizing bisphenol sulfoxide, a method of oxidizing 4, 4'-bisphenol sulfoxide with hydrogen peroxide in glacial acetic acid to obtain a corresponding sulfone, such as 4, 4'-diphenol sulfoxide Oxidation in excess glacial acetic acid at 85 ° C. to obtain the final target in 85% yield (LM Nikolenko. Et al, J. General Chem. Of USSR, 33, 3731 (1963).

(5) There is no known oxidation of 2,2'-bisphenol sulfoxide, and 2,2'-bisphenol sulfoxide is produced by peracetic acid oxidation, as in the aforementioned 4, 4'-bisphenol sulfoxide. It is expected that only 2, 2'-bisphenol sulfone derivatives are produced.

However, in the above-mentioned methods (2), (4) and (5), the oxidation reaction is carried out in an excess of peracetic acid, and there is a risk of explosion due to the occurrence of dolby (시) during handling, and the excess glacial acetic acid. Excess wastewater is used to discharge the wastewater, which requires a lot of expenses due to wastewater treatment, and has many drawbacks in terms of operations and economics to perform these reactions on an industrial scale.

In the case of the above-mentioned method (3), since the metal catalysts used are quite expensive and are dissolved in an aqueous solution, their recovery operation is quite complicated, and there are many problems due to environmental pollution, and especially reaction conditions such as pH. It is not industrially considered an economical or effective method because it has a significant effect on the yield and purity of the final target, or the target is colored.

It is an object of the present invention to provide a novel and industrially effective method for producing a bisphenol sulfone derivative.

It is another object of the present invention to provide a method for preparing a high purity bisphenol sulfone in high yield.

According to the present invention, the above-mentioned compounds are oxidized with hydrogen peroxide in the presence of an alkali at least equimolar to the compound represented by the following general formula (II) in an organic solvent which does not produce any organic peracid under reaction conditions and a solvent selected from water. There is provided a method for producing a bisphenol sulfone derivative characterized by producing a bisphenol sulfone derivative characterized by producing a bisphenol sulfone derivative represented by formula (I).

(Wherein R represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxyl group, an alkoxy group, an allyloxy group, a carboxyl group, or a carboalkoxy group, m is an integer of 1 to 3) When m is 2 or more, R may be the same or different from each other, or may be bonded to adjacent Rs to form a ring, and n is 0 or 1).

According to the present invention, the compound represented by the general formula (II), that is, bisphenol sulfide (when n = 0 in the general formula (II)) and bisphenol sulfoxide (n = 1 in the general formula (II) Is an equivalent molar or more alkali to the raw material producing the solution to produce the corresponding phenolola art. When phenololat is reacted with the theoretical amount of hydrogen peroxide, an ideal oxidation reaction proceeds, and the reaction mixture is neutralized after the reaction is completed to obtain a bisphenol sulfone derivative.

According to the present invention, when phenol laart is insoluble in water, the bisphenol sulfide or bisphenol sulfoxide represented by the above general formula (II) is contained in a small amount of organic solvent which does not produce any organic peracid by the reaction of hydrogen peroxide. The reaction can be carried out by dissolving phenololat.

In addition, regardless of the solubility of phenollaart in water, using an organic solvent instead of water is sufficient even if a smaller amount of organic solvent is used compared to the amount of water used. It can be greatly improved.

Alkaline should be used in an amount greater than or equal to these with respect to bisphenol sulfide or bisphenol sulfoxide, and in the absence of alkali, the reaction will not proceed.

In the case of bisphenol sulfide, sulfoxide is mixed when alkali is used in an amount less than equimolar, but sulfone is produced in proportion to the amount of alkali used, and sulfoxide is lost when equimolar use of alkali is used to form sulfone.

In the case of bisphenol sulfoxide, sulfone is produced in proportion to the amount of alkali added to the sulfoxide, and all of the sulfones are produced by using the alkali in an equimolar amount.

As alkali used for this invention, alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, can be illustrated, Alkali may use a solid form directly, Usually, it is used as a form of aqueous solution. In addition, alkali is usually used in an amount of equimolar to 5 moles, preferably equimolar to 2 moles, relative to the compound represented by the general formula (II). However, in the case of bisphenol having a carboxyl group (S) as a substituent, an alkali equivalent of carboxyl group is added to form an alkali metal salt of carboxylic acid, and then an alkali of not less than equimolar is added thereto, and the amount of alkali used is adjusted to adjust phenol. You have to create art.

As a compound represented by the said General formula (II), 2, 2'-bisphenol sulfoxide, 2, 2'-bisphenol compound represented by following General formula (III), such as 2, 2'-bisphenol sulfoxide, and 4 And 4,4'-bisphenol compounds represented by the following general formula (IV) such as 4'-bisphenol sulfide and 4, 4'-bisphenol sulfoxide.

In the above formulas, R ₁ , R ₂ and R ₃ are the same or different from each other, and hydrogen, halogen, alkyl, cycloalkyl, aryl, aralkyl, hydroxyl, alkoxy, allyloxy, carboxyl or carboalkoxy R ₁ and R ₂ R ₂ and R ₃ or R _{1, 2} and R ₃ may form a ring together with the carbon atoms of the Belsen nucleus to which R ₁ R ₂ and R ₃ are bonded, respectively; ₄ and R ₅ have the same meaning as R ₁ , R ₂ as defined above, and n is 9 or 1).

More specifically, the above-mentioned compounds are exemplified by 2, 2'-bisphenol sulfide, such as 2, 2'-diphenol sulfide 2, 2'-bis (4-methylphenol) sulfide, 2, 2 '-Bis (6-methylphenol) sulfide, 2, 2'-bis (4-iso-propylphenol) sulfide, 2, 2'-bis (4-n-butylphenol) sulfide, 2, 2' -Bis (4-third-butylphenol) sulfide, 2,2'-bis (4-third-butylphenol) sulfide, 2,2'-bis (6-third-butylphenol) sulfide, 2, 2'-bis (4-third-amylphenol) sulfide, 2, 2'-bis (4-third-octylphenol) sulfide, 2, 2'-bis (4-nonyl-phenol) sulfide Feed, 2, 2'-bis (4-O3-butyl-6-methylphenol) sulfide, 2, 2'-bis (4-methyl-6-third-butylphenol) sulfide, 2, 2'- Bis (4, 6-dimethylphenol) sulfide, 2, 2'-bis (4, 6-di-third-butylphenol) sulfide, 2, 2'-bis (4, 5-dimethylphenol) sulfide , 2, 2'-bis (4-cyclohexylphenol) sulfide, 2, 2'-bis (4-cyclohexyl-6-methylphenol) sulfide, 2, 2'-bis (4, 6-dichlorohexyl -Phenol) sulfide, 2, 2'-bis (4-α α'-dimethyl-benzylphenol) sulfide, 2, 2'-bis (4-benzylphenol) sulfide, 2, 2'-bis (4, 6-dibenzylphenol) sulfide, 2, 2'-bis (4-phenylphenol) sulfide, 2, 2'-bis (4-phenyl-6-methylphenol) sulfide, 2, 2'-bis (4-α, α'-dimethylbenzyl-6-phenylphenol) Sulfide, 2, 2'-bis (4-chlorophenol) sulfide, 2, 2'-bis (4, 6-dichlorophenol) sulfide, 2, 2'-bis (4, 5, 6-trichloro Phenol) sulfide, 2, 2'-bis (4-bromophenol) sulfide, 2, 2'-bis (4, 6-dibromophenol) sulfide, 2, 2'-bis (4-hydride Oxyphenol) sulfide, 2, 2'-bis (4, 6-dimethoxyphenol) sulfide, 2, 2'-bis (4-carboxyphenol) sulfide, 2, 2'-bis (4-carbome Oxyphenol) sulfide, 2, 2'-bi (4-scarbobutoxyphenol) sulfide, 1, 1'-bis (2-naphthol) sulfide, 2, 2'-bis (1-naphthol) Feeds, such as 2, 2'-bisphenol sulfoxide such as 2, 2'-diphenol sulfoxide, 2, 2'-bis (4-methylphenol) sulfoxide, 2, 2'-bis (6-methylphenol) Sulfoxide, 2, 2'-bis (4-iso-propylphenol) sulfoxide, 2, 2'-bis (4-n-butylphenol) sulfoxide, 2, 2'-bis (4-second 2-butylphenol) sulfoxide Seed, 2, 2'-bis (4-third-butylphenol) sulfoxide, 2, 2'-bis (6-third-butylphenol) sulfoxide, 2, 2'-bis (4-third- Butylphenol) sulfoxide, 2, 2'-bis (4-ze3-amylphenol) sulfoxide, 2 2'-bis (4-ze3-octylphenol) sulfoxide, 2 2'-bis (4-nonyl Phenol) sulfoxide, 2, 2'-bis (4-third-butyl-6-methylphenol) sulfoxide, 2, 2'-bis (4-methyl-6-third-butylphenol) sulfoxide, 2 , 2'-bis (4, 6-dimethylphenol) sulfoxide, 2, 2'-bis (4, 6-di-thi-butylphenol) sulfoxide, 2, 2'-bis (4, 5-dimethyl Phenol) sulfoxide, 2, 2'-bis (4-cyclohexylphenol) sulfoxide, 2, 2'-bis (4-cyclohexyl-6-methylphenol) sulfoxide, 2, 2'-bis (4, 6-dicyclohexylmethylphenol) sulfoxide, 2, 2'-bis (4-α, α'-dimethyl benzylphenol) sulfoxide, 2, 2'-bis (4-benzylphenol) sulfoxide, 2, 2'-bis (4, 6-D Nitrophenol) sulfoxide, 2, 2'-bis (4-phenylphenol) sulfoxide, 2, 2'-bis (4-phenyl-6-methylphenol) sulfoxide, 2, 2'-bis (4-α , α'-dimethylbenzyl-6-phenylphenol) sulfoxide, 2, 2'-bis (4-chlorophenol) sulfoxide, 2, 2'-bis (4, 6-dichlorophenol) sulfoxide, 2, 2 -Bis (4, 5, 6-trichlorophenol) sulfoxide, 2 2'-bis (4-bromophenol) sulfoxide, 2, 2'-bis (4, 6-dibromophenol) sulfoxide, 2, 2'-bis (4-hydroxyphenol sulfoxide, 2, 2'-bis (4, 6-dimethylphenol) sulfoxide, 2, 2'-bis (4-carboxyphenol) sulfoxide, 2, 2 '-Bis (4-carbomethoxyphenol) sulfoxide, 2, 2'-bis (4-carbomethoxyphenol) sulfoxide, 1, 1'-bis (2-naphthol) sulfoxide, 2, 2'- 4 4'-bisphenolsulfide, such as 4, 4'-diphenolsulfide, 4, 4'-bis (2-chlorophenol) sulfide, 4, 4'-bis, such as bis (1-naphthol) sulfoxide (3-chlorophenol) sulfide, 4, 4'-bis (2-methylphenol) sulfide, 4, 4'-bis (3-methylphene ) Sulfide, 4, 4'-bis (2, 5-dimethylphenol) sulfide, 4, 4'-bis (2-isopropyl-5-methylphenol) sulfide, 4, 4'-bis (2- Methyl-6-third-butylphenol) sulfide, 4, 4'-bis (2, 6-di-third-butylphenol) sulfide, 4, 4'-bis (2-hydroxyphenol) sulfide 4, 4'-bisphenol sulfoxides, such as 4, 4'-bis (2-cartoxyphenol) sulfide, 4, 4'-bis (2-carbomexoxyphenol) sulfide, such as 4, 4'-di Phenol sulfoxide, 4, 4'-bis (2, 5-dimethylphenol) sulfoxide, 4, 4'-bis (2-third-butyl-phenol) sulfoxide, 4, 4'-bis (2-cyclo Hexylphenol) sulfoxide, 4, 4'-bis (2-third-butyl-5-methylphenol) sulfoxide, 4, 4'-bis (2-benzylphenol) sulfoxide, 4, 4'-bis ( 2-methoxyphenol) sulfoxide, 4, 4'-bis (2-phenoxyphenol) sulfoxide, 4, 4'-bis (carboxyphenol) sulfoxide, 4, 4'-bis (2-carbomethoxy Phenol) sulfoxide and the like.

The process of the present invention is usually carried out in an aqueous medium, and an organic solvent can be used in place of water, regardless of the solubility of phenoluraart in water.

Examples of the organic solvent used in the method of the present invention include known organic solvents except organic acids in which organic peracids are formed by hydrogen peroxide under reaction conditions, more specifically aliphatic such as hexanecyclohexane, heptane, benzene, toluene, xylene and ethylbenzene. Aliphatic, cycloaliphatic and aromatic halogenated hydrocarbons such as cycloaliphatic and aromatic cyclohydrocarbons, dichloromethane, chloroform, carbon tetrachloride, dichloroethane trichloroethane, chlorobenzene and 0-dichlorobenzene, methanol, ethanol, propanol and butanol Alcohols such as diethyl ether, dibutyl ether, ethers such as tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone, esters such as dissipative esters and propionic acid esters, and N.N-dimethylformamide Aprotic polar solvents such as, dimethyl sulfoxide and N-methyl pitolidon and carbon disulfide can be exemplified. have.

The solvents mentioned above can be used in the form of a mixture of these or a mixture of these and water.

Among the solvents mentioned above, hydrocarbons and halogenated hydrocarbon solvents which are not miscible with water, such as benzene, toluene, xylene, chlorobenzene, dichloroethane and carbon tetrachloride, can be recovered by steam distillation after the reaction is completed. In addition, the solvents thus recovered are circulated and reused directly, or if necessary, after refining operations such as distillation are reused to reduce the amount of solvent used, thereby reducing costs and reducing environmental problems. The industrial effect is great because it can be made.

The usage-amount of a solvent is 0.5 to 10 volume parts normally with respect to 1 weight part of raw material sulfides, and about 2 to 5 volume parts are preferable.

Hydrogen peroxide is used as an aqueous solution of hydrogen peroxide at various concentrations. For ease of handling, it is preferable to use an aqueous hydrogen peroxide solution at a concentration of 30 to 35%.

In addition, hydrogen peroxide is usually used slightly in excess of the theoretical value required for bisphenol, and can be used in an amount of 1.5 to 5.0 times higher than the theoretical value.

Oxidation reaction with hydrogen peroxide is carried out by dropwise addition of hydrogen peroxide to the solution of the sulfoxide and alkali, or by adding and mixing hydrogen peroxide in advance in the solution.

The reaction according to the present invention is usually carried out at a temperature of 30 to 110 ℃, when the reaction temperature is less than 30 ℃ should be carried out for a long time, and when the reaction temperature exceeds 110 ℃, the concentration of hydrogen peroxide is extremely reduced As a result, adverse effects such as Dolby occur, which prevents the reaction from continuing. Therefore, the reaction temperature is preferably in the range of 50 to 100 ° C.

In carrying out the method of the present invention, bisphenol and equimolar alkalis are usually dissolved in water and (or an organic solvent), and the aqueous solution of hydrogen peroxide is added dropwise thereto while maintaining the solution at a temperature of 30 to 110 占 폚. After completion of the dropwise addition of the aqueous solution, the resulting reaction mixture was stirred at the above temperature for 30 minutes to 5 hours, cooled to room temperature, and then neutralized by adding acid directly, followed by dilution with water. Or distillation of the solvent by neutralization of the solvent, or by direct steam distillation of the reaction mixture of the alkaline solution, followed by neutralization.

The resulting precipitate is filtered off, washed with water and dried to obtain the final desired bisphenol sulfone derivative.

In any of the above-described cases, a high-purity target that can be used directly as a light stabilizer, a polyolefin regulator, a lubricant additive, an agricultural chemical, or an intermediate thereof can be obtained with a high yield of 95% or more without performing further further operations.

Bispanol sulfoxide used in the present invention can be prepared by a conventional method, for example, by reacting a substituted phenol with thionyl chloride in the presence of anhydrous aluminum chloride.

According to the present invention, the present oxidation reaction is preferably carried out using the theoretical amount of hydrogen peroxide, even if excess hydrogen peroxide is used, there is no problem, and according to the method of the present invention, other by-products resulting from the oxidation reaction are also produced. The industrial effect is great because extremely high purity of the corresponding bisphenol sulfone derivatives are obtained in almost quantitative yield.

The present invention will be described in more detail with reference to the following examples.

Example 1

24.6 g (0.1 mol) of 2,2'-bis (4-methylphenol) sulfide was dissolved in a solution of 6 g (0.15 mol) of sodium hydroxide and 100 ml of water, and the solution was maintained at a temperature of 70 to 75 ° C. In addition, 28.3 g (0.25 mol) of 30% aqueous hydrogen peroxide solution was added dropwise thereto over 30 minutes.

The resulting reaction mixture was stirred at this temperature for another 1 hour, and then diluted by adding 100 ml of water.

The resulting solution was then cooled to room temperature and overloaded to yield no precipitate. The precipitate was filtered off, washed with water and dried to give 26.8 g (yield, 96.4% of theory) of 2,2'-bis (4-methylphenol) sulfone having a melting point of 205 to 206 占 폚. Further, the precipitate was recrystallized in glacial acetic acid to obtain the pure target of white needle crystal having a melting point of 207 to 208 占 폚.

Elemental analysis of this compound is as follows.

Example 2

26.2 g (0.1 mol) of 2,2'-bis (4-methylphenol) sulfoxide was dissolved in a solution of 5 g (0.125 mol) of sodium hydroxide and 100 ml of water, and the solution was maintained at a temperature of 70 to 75 ° C. Then, 17 g (0.15 mol) of 30% aqueous hydrogen peroxide solution was added dropwise over 30 minutes. The resulting reaction mixture was stirred at this temperature for 1 hour and then diluted by adding 100 ml of water thereto.

Next, the resulting solution was cooled to room temperature and then neutralized to precipitate. The resulting precipitate was filtered off, washed with water and dried to give 27.1 g (yield, 97.5% of theory) of 2,2'-bis (4-methylphenol) sulfone having a melting point of 205 to 206 占 폚.

Example 3

28.7 g (0.1 mol) of 2,2'-bis (4-chlorophenol) sulfide was dissolved in 40 ml of ethanol, and 20 g (0.15 mol) of 30% aqueous hydrogen peroxide solution was added to the resulting solution, followed by temperature of 65 to While maintaining at 70 ° C, 28.3 g (0.25 mol) of 30% aqueous hydrogen peroxide solution was added dropwise over 30 minutes. The resulting reaction mixture was stirred at this temperature for another 1 hour, and then diluted by adding 50 ml of water thereto. The resulting solution was then cooled to room temperature and neutralized to yield a precipitate. The resulting precipitate was filtered off, washed with water and dried to give 30.9 g (yield, 97% of theory) of 2,2'-bis (4-chlorophenol) sulfone having a melting point of 189 to 190 占 폚. This precipitate was further recrystallized in glacial acetic acid to obtain the pure target of white needle crystal.

Elemental analysis of this compound is as follows.

[Examples 4-9]

Except for using 2,2'-bisphenol, the operation of Example 3 was repeated to obtain the corresponding bisphenol sulfone having the results described in the first table.

[Table 1]

※ The values in parentheses indicate the calculated values.

Example 10

33 g (0.1 mol) of 2,2'-bis (4-thi-butylphenol) sulfide was dissolved in 50 ml of 1, 2-dichloroethane, and 20 g (0.15 mol) of 30% aqueous hydrogen peroxide solution was added to the resulting solution. After the addition, 28.3 g (0.25 mol) of 30% aqueous hydrogen peroxide solution was added dropwise over 30 minutes while maintaining the temperature of the solution at a temperature of 45 to 50 ° C.

The reaction mixture was then stirred for 3 hours at the above temperature and then neutralized. Next, the reaction mixture was subjected to steam distillation to distill 1, 2-dichloroethane to form a precipitate. Next, after cooling to room temperature, the precipitate was filtered off, washed with water and dried to give 35.5 g of 2,2'-bis (4-tert-butylphenol) sulfone having a melting point of 129 to 130 ° C (yield, theoretical value). 98%) was obtained.

This precipitate was further recrystallized in n-hexane to obtain the pure target of white needle crystal with melting point of 131-132.5 degreeC.

Elemental analysis of this compound is as follows.

Example 11

The procedure of Example 10 was repeated except that 2, 2'-bis (4, 6-dichlorophenol) sulfide was used, and 2, 2'-bis (4, 6-dichlorophenol having a melting point of 168 to 170 ° C. ) Sulfone was obtained in a yield of 96%.

The product thus obtained was further recrystallized in ethanol, whereby a pure target of white needle crystal having a melting point of 170 to 171 캜 was obtained.

Elemental analysis of this compound is as follows.

Example 12

2,2'-bis (4-third-octylphenol) sulfide 44.2 g (0.1 mole), 20% hydrogen peroxide aqueous solution 30 g (0.15 mole), 30% hydrogen peroxide aqueous solution 28.3 g (0.25 mole) and mixed with 60 ml benzene The mixture was stirred at a temperature of 70 to 75 ° C. for 3 hours and then steam distilled to distill benzene.

The reaction mixture was then thickened to yield a precipitate. The resulting precipitate was filtered off, washed with water and dried to obtain 46.6 g of 2,2'-bis (4-thi-3-octylphenol) sulfone having a melting point of 142 to 143 ° C (yield, 95.5% of theory). lost.

This compound was further recrystallized in glacial acetic acid to give the pure target of the white needle crystal with a freezing point of 143-145 degreeC.

Elemental analysis of this compound is as follows.

Example 13

Except for using 2,2'-bis (4-methyl-6-third-butylphenol) sulfide, the operation of Example 12 was repeated to give 2,2'-bis (4 having a melting point of 130 to 131 ° C. -Methyl-6-third-butylphenol) sulfone (yield, 95.5%) was obtained.

The above-mentioned product was further recrystallized in ethanol to obtain the pure target of white needle crystal with melting point of 132 to 134 占 폚.

The elemental analysis of this compound is as follows.

Example 14

35.8 g (0.1 mol) of 2,2'-bis (4-third-amylphenol) sulfide was dissolved in 30 ml of chlorobenzene, and 20% hydrogen peroxide and 36.5 g (0.13 mol) of an aqueous solution were added to the solution.

Next, while maintaining the temperature of this solution at 75-80 degreeC, 28.3 g (0.25 mol) of 30% aqueous hydrogen peroxide aqueous solutions were added dropwise over 30 minutes. Next, the reaction mixture was stirred at the above temperature for another 1 hour and then neutralized.

Next, the reaction mixture was subjected to steam distillation to distill chlorobenzene to form a precipitate. Next, after cooling to room temperature, the resulting precipitate was filtered off, washed with water and dried to obtain 37.6 g of 2,2'-bis (4-thi-amylphenol) sulfone having a melting point of 117 to 118 ° C (yield, 96.5% of theory) was obtained.

This product was further recrystallized in n-hexane to obtain the pure target as a white free symptom crystal having a melting point of 119 to 120 ° C.

Elemental analysis of this chemical is as follows.

Example 15

29.3 g (0.1 mol) of 2,2'-bis (4-chlorophenol) was dissolved in 40 ml of ethanol, and 20 g (0.15 mol) of 30% aqueous hydrogen peroxide solution was added to the solution, and then the temperature of the solution was 65 to 17 g (0.15 mol) of 30% aqueous hydrogen peroxide solution was added dropwise over 30 minutes while maintaining the temperature at 70 占 폚. The resulting reaction mixture was stirred at this temperature for another 1 hour, and then diluted by adding 50 ml of water.

After cooling to room temperature, the reaction mixture was neutralized to precipitate. The resulting precipitate was filtered off, washed with water and then dried to give 31.2 g (yield, 98% of theory) of 2,2′-bis (4-chlorophenol) sulfone having a melting point of 190 to 191 ° C.

Example 16

Except for using 2 2'-bis (4-bromophenol) sulfoxide, the operation of Example 15 was repeated to give 2,2'-bis (4-bromophenol) sulfone having a melting point of 207 to 208 캜. Yield 97%).

Example 17

34.6 g (0.1 mol) of 2,2'-bis (4-tert-butylphenol) sulfide was dissolved in 50 ml of 1, 2-dichloroethane, and 20 g (0.15 mol) of aqueous hydrogen peroxide solution was added to the solution. And 17g (0.15 mol) of 30% aqueous hydrogen peroxide aqueous solution was added dropwise over 30 minutes, maintaining the temperature of this solution at the temperature of 40-50 degreeC.

The resulting reaction mixture was stirred for 3 hours at this temperature and then neutralized. Next, the reaction mixture was further steam distilled to produce a precipitate.

After cooling to room temperature, the resulting precipitate was filtered off, washed with water and dried to give 35.6 g of 2 2'-bis (4-tert-butylphenol) sulfone having a melting point of 130 to 132 캜 (yield, theoretical value). 98.5%) was obtained.

Example 18

The procedure of Example 17 was repeated except that 2, 2'-bis (4, 6-dichlorophenol) sulfoxide was used, and 2, 2'-bis (4, 6-dichlorophenol having a melting point of 169 to 170 ° C. ) Sulfone (yield 97.5%) was obtained.

Example 19

45.8 g (0.1 mol) of 2,2'-bis (4-thi-octylphenol) sulfoxide, 30 g (0.15 mol) of 20% aqueous hydrogen peroxide solution, 17 g (0.15 mol) of 30% aqueous hydrogen peroxide solution, and 60 ml of benzene The mixture was stirred at a temperature of 70 to 75 ° C. for 3 hours, and the resulting reaction mixture was subjected to steam distillation to distill benzene.

Next, the reaction mixture was cooled and precipitated. After cooling to room temperature, the resulting precipitate was filtered off, washed with water and dried to give 46.9 g of 2,2'-bis (4-thi-octylphenol) sulfone having a melting point of 142 to 143 ° C (yield, 99% of theory) was obtained.

Example 20

Except for using 2,2'-bis (4-methyl-6-third-butylphenol) sulfoxide, the operation of Example 19 was repeated to give 2,2'-bis having a melting point of 130 to 131 ° C. -Methyl-6-third-butylphenol) sulfone was obtained.

Example 21

37.4 g (0.1 mol) of 2,2'-bis (4-thi-amylphenol) sulfoxide was dissolved in 30 ml of chlorobenzene, and 20% hydrogen peroxide was added thereto while maintaining the temperature of the solution at 75 to 80 ° C. An aqueous solution of 36.5 g (0.13 mol) was added and then 17 g (0.15 mol) of 30% aqueous hydrogen peroxide solution was added dropwise over 30 minutes.

The resulting reaction mixture was stirred for 1 hour at this temperature and then neutralized. The reaction mixture was further steam distilled to distill chlorobenzene to form a precipitate. After cooling to room temperature, the resulting precipitate was filtered off, washed with water and dried to give 38 g of 2,2'-bis (4-thi-amylphenol) sulfone having a melting point of 117 to 118 ° C (yield, 97.5 of theory). %) Was obtained.

Example 22

21.8 g (0.1 mol) of 4,4'-bisphenol sulfide was dissolved in a mixture of 5 g (0.125 mol) of sodium hydroxide and 100 ml of water, and 30% aqueous hydrogen peroxide solution was maintained while maintaining the temperature of the solution at 60 to 65 ° C. 28.3 g (0.25 mol) was added dropwise over 30 minutes.

The resulting reaction mixture was stirred at this temperature for 2 hours, cooled to room temperature, and then neutralized. The precipitate was formed.

The resulting precipitate was filtered off, washed with water and dried to give 23.5 g of 4,4'-diphenol sulfone having a melting point of 245 to 246 占 폚 (yield 94%).

This product was further recrystallized in water to give the pure target of white needle crystal with melting point of 247 to 248 占 폚.

[Examples 22-25]

The procedure of Example 22 was repeated except that 4, 4'-bisphenol sulfide was used to give the corresponding sulfone having the results described below.

Example 26

A solution in which 27.7 g (0.1 mol) of 4,4'-bis (2-chlorophenol) sulfide was dissolved in 80 ml of ethanol and 5 g (0.125 mol) of sodium hydroxide in 20 ml of water was added to the solution. 28.3 g (0.25 mol) of 30% aqueous hydrogen peroxide solution was added dropwise to the solution over 30 minutes while maintaining the temperature of the resulting solution at a temperature of 70 to 75 ° C. The reaction mixture was stirred at this temperature for another 2 hours, cooled to room temperature, and the reaction mixture was neutralized to precipitate. The resulting precipitate was filtered off, washed with water and dried to give 29.0 g (yield, 94% of theory) of 4,4'-bis (2-chlorophenol) sulfone having a melting point of 195 to 197 ° C.

The product was recrystallized from a mixture of ethanol and water to obtain a pure target product having a melting point of 196 to 197 ° C of white needle crystals.

[Examples 27-28]

The procedure of Example 26 was repeated except that 4, 4'-bisphenol sulfide was used as the starting material to obtain the corresponding sulfone having the results described below.

Example 29

23.4 g (0.1 mol) of 4,4'-diphenol sulfoxide was dissolved in a solution of 7.0 g (0.125 mol) of potassium hydroxide and 100 ml of water, and the temperature of the solution was maintained at a temperature of 55 to 60 DEG C. 14.2 g (0.125 mol) of 30% aqueous hydrogen peroxide solution was added dropwise over 30 minutes. The resulting reaction mixture was stirred at this temperature for another 3 hours, cooled, and then neutralized. The precipitate was formed.

The resulting precipitate was filtered off, washed with cold water and dried to give 23.9 g (4% of theory, 96%) of 4,4'-diphenol sulfone.

Example 30

36.5% (0.13 mol) of 20% aqueous hydrogen peroxide solution was added to a solution of 37.4 g (0.1 mol) of 4,4'-bis (2-third-butyl-5-methylphenol) sulfoxide in 150 ml of xylene. While maintaining the temperature of this solution at 75 to 80 ° C., 14.2 g (0.125 mol) of 30% aqueous hydrogen peroxide solution was added dropwise over 30 minutes. The resulting reaction mixture was stirred at this temperature for another 2 hours and then neutralized. The reaction mixture was further distilled off under water to distill xylene to form precipitates.

After cooling to room temperature, the resulting precipitate was filtered off, washed with water and dried to give 38.0 g of 4,4'-bis (2-tert-butyl-5-methylphenol) sulfone having a melting point of 248 to 250 캜. Yield, 98% of theory). This product was further recrystallized in ethanol to obtain a pure target having a melting point of white needle crystals of 250 to 251 占 폚.

[Examples 31 to 32]

The procedure of Example 30 was repeated except that 4, 4'-diphenol sulfoxide was used as a starting material to obtain the corresponding sulfone having the results described below.

Example 33

32.2 g (0.1 mole) of 4,4'-bis (2-carboxyphenol) sulfoxide was dissolved in a solution of 13.2 g (0.33 mole) of sodium hydroxide and 150 ml of water, and the oxo of the solution was maintained at 50 to 60 ° C. To this was added dropwise 14.2 g (0.125 mol) of 30% aqueous hydrogen peroxide solution. Next, the reaction mixture was stirred at the above-mentioned temperature for another 4 hours, cooled to room temperature, and the reaction mixture was neutralized to precipitate. The resulting precipitate was filtered off, washed with water and dried to obtain 33 g (yield, 97.5% of theory) of 4,4'-bis (2-carboxyphenol) sulfone having a melting point of 301 to 303 ° C.

This product was further recrystallized in a mixture of dissipation and water to give the pure target of white needle crystal with melting point of 303 to 304 °.

Claims (1)

The above compound in the presence of an organic solvent which does not produce any organic peracid and water under the reaction conditions for forming the bisphenol sulfone derivative, and an alkali in an equimolar amount or more relative to the compound represented by the following general formula (II). A method for producing a bisphenol sulfone derivative characterized by producing a bisphenol sulfone derivative represented by the following general formula (I) by oxidizing with hydrogen peroxide.

(Wherein R represents a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an aryl group, an aralkyl group, a hydroxyl group, an alkoxy group, an allyloxy group, a carboxyl group or a carboalkoxy group, m is an integer of 1 to 3, when m is 2 or more, R may be the same or different from each other, or may combine with adjacent Rs to form a ring, and n is 0 or 1).