KR830001715B1 - Method for preparing 2,2'-bisphenol sulfoxide - Google Patents

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Description

Method for preparing 2,2'-bisphenol sulfoxide

The present invention relates to a method for preparing 2,2'-bisphenol sulfoxide.

In general, it is almost impossible to generate only sulfoxide in the oxidation reaction of an aromatic sulfide, and a problem arises in that sulfone is incorporated into the reaction mixture layer as a by-product. Therefore, in order to prevent the formation of sulfones due to side reactions and to produce only high selectivity of sulfoxide, N-bromosuccinimide, diazabicyclo [2,2,2] -octane bromine complex, pyridine, It has been recommended to use only certain oxidants such as quinoline.

In the oxidation reaction of aromatic sulfide by hydrogen peroxide, glacial acetic acid (peracetic acid oxidation) has been widely used as a solvent, but since sulfoxide itself is easily oxidized by hydrogen peroxide to form sulfone, even if the theoretical amount of hydrogen peroxide is used, For example, it is difficult to selectively prepare only sulfoxide.

That is, in most cases the method of oxidizing aromatic sulfides with hydrogen peroxide is a method that is substantially employed to prepare the corresponding sulfones. It is known that the corresponding 2,2'-bisphenol sulfones are obtained which oxidize 2,2'-bisophenol sulfide to hydrogen peroxide in the presence of glacial acetic acid. J. Am. Chem. Soc., 67, 238 (1966).

It is an object of the present invention to oxidize 2,2'-bisphenolsulfide to produce almost no by-product and to obtain the corresponding 2,2'-bisphenol sulfoxide in high yield. It is to provide a method of manufacturing.

The present inventors have extensively studied the oxidation reaction of 2,2'-bisphenol sulfide with hydrogen peroxide from the viewpoint of hydrogen peroxide being a preferable oxidant because of its low cost, easy handling, and easier post-reaction treatment. As a result, 2,2 'is commercially available by performing oxidation reaction of 2,2'-bisphenolsulfide with hydrogen peroxide in the presence of a known organic solvent, except for organic acids such as glacial acetic acid and formic acid, which produce organic peracids by hydrogen peroxide. It was found that bisphenol sulfoxide could be prepared.

That is, the method of the present invention is 2,2'-bisphenol sulfide in the presence of an organic solvent which does not produce any organic peracid under the reaction conditions, preferably 2,2'-bisphenol sulfide represented by the following general formula (II) A method for producing a 2,2'-bisphenol sulfoxide, preferably 2,2'-bisphenol sulfoxide, characterized by oxidizing a feed with hydrogen peroxide.

Wherein R ₁ , R ₂ and R ₃ are selected from 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 and a carboalkoxy group R ₁ and R ₂ , R ₂ and R _3, or R ₁ , R ₂ and R ₃ , together with the carbon atoms of the benzene nucleus to which these groups are bound, form a ring).

According to the present invention, the present oxidation reaction is preferably carried out using the theoretical amount of hydrogen peroxide. Even when an excessive amount of hydrogen peroxide is used, no sulfone is produced, and no other by-products due to the oxidation reaction are generated, and extremely high purity is achieved. The industrial effect is large because the corresponding bisphenol sulfoxide of is obtained in near quantitative yield.

In the method of this invention, it is preferable to use the compound represented by following General formula (II) for 2,2'-bisphenol sulfide.

Wherein R ₁ , R ₂ and R ₃ are selected from hydrogen atom, halogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, hydroxyl group, alkoxy group, allyloxy group, carboxyl group and carboalkoxy group ₁ and R ₂ , R ₂ and R ₃ or R ₁ , R ₂ and R ₃ may form a ring together with the carbon atoms of the benzene nucleus to which these groups are bonded, respectively.)

Illustrating the compounds mentioned above

2,2'-diphenol sulfide, 2,2'-bis (4-methylphenol) sulfide, 2,2'-bis (6-methylphenol) sulfide, 2,2'-bis (4-iso -Propyl phenol) sulfide, 2,2'-bis (4-n-butylphenol) sulfide, 2,2'-bis (4-second 2-butylphenol) sulfide,

2,2'-bis (4-third-butylphenol) sulfide, 2,2'-bis- (6-third-butylphenol) sulfide, 2,2'-bis (4-third-mild Phenol) sulfide, 2,2'-bis (4-third-octylphenol) sulfide, 2,2'-bis (4-nonylphenol) sulfide, 2,2'-bis (4- agent 3- Butyl-6-methylphenol) sulfide, 2,2'-bis (4,6-methyl-6-third-butylphenol) sulfide, 2,2'-bis (4,6-dimethylphenol) sulfide , 2,2'-bis (4,6-di-zet-butylphenol) sulfide, 2,2'-bis (4,5-dimethylphenol) sulfide, 2,2'-bis (4-cyclo Hexylphenol) sulfide, 2,2'-bis (4-cyclohexyl-6-methylphenol) sulfide, 2,2'-bis (4,6-dicyclohexylphenol) sulfide, 2,2'- Bis (4-α, α'-dimethylbenzylphenol) 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) sulphate Feed, 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-trichlorophenol) sulfide, 2,2'-bis (4-bromophenol) Sulfide, 2,2'-bis (4,6-dibromophenol) sulfide, 2,2'-bis (4-hydroxyphenol) sulfide, 2,2'-bis (4,6-dimeth Oxyphenol) sulfide, 2,2'-bis (4-carboxyphenol) sulfide, 2,2'-bis (4-carbomethoxyphenol) sulfide, 2,2'-bis (4-carbobutoxy Phenol) sulfide, 1,1'-bis (2-naphthol) sulfide, 2,2'-bis (1-naphthol) sulfide, and the like.

Examples of the organic solvent used in the method of the present invention include known organic solvents other than organic acids which generate organic peracids by hydrogen peroxide, more specifically hydrocarbons such as hexane, cyclohexane, heptane, benzene, toluene, xylene and ethylbenzene, Halogenated hydrocarbons such as trichloromethane, chloroform, carbon tetrachloride, tichloroethane, trichloroethane, chlorobenzene and 0-dichlorobenzene, alcohols such as methanol, ethanol, propanol and butane, dietyl ether, dibutyl Ethers such as ether, tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone, esters such as ester and propionic acid esters, N, N-dimethylformamide, dimethyl sulfoxide and N-methyl Aprotic solvents such as pyrrolidone, and carbon disulfide.

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 described 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 can be circulated and reused directly, or, if necessary, used again for purification operations such as distillation, thereby reducing costs by reducing the amount of solvent used, and also reducing environmental problems. Therefore, the industrial effect is great.

The amount of the solvent used is usually 0.5 to 10 vol parts based on 1 part by weight of the raw material sulfide, and preferably about 2 to 5 vol parts.

Hydrogen peroxide is used as an aqueous hydrogen peroxide solution of various concentrations, but it is preferable to use an aqueous hydrogen peroxide solution at a concentration of 30 to 35% because of easy handling. Hydrogen peroxide is usually used slightly in excess of the theoretical value, and may be used in an amount of 1.5 to 5.0 times higher than the theoretical value.

The oxidation reaction with hydrogen peroxide is carried out by dropwise addition of hydrogen peroxide to the solution of sulfide and solvent, or by adding and mixing hydrogen peroxide in advance to 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 30 ℃ or less, the reaction must be carried out for a long time, and when the reaction temperature exceeds 110 ℃, the concentration of hydrogen peroxide is extremely Reduction of adverse effects, such as bubbles, is hampered by continued reaction. Therefore, the reaction temperature is preferably in the range of 50 to 110 ° C.

In carrying out the method of the present invention, 2,2'-bisphenol sulfide is usually dissolved in the solvent described above, the solution is maintained at a temperature of 30 to 110 占 폚, and then aqueous hydrogen peroxide solution is added dropwise thereto. After completion of the dropwise addition of the aqueous hydrogen peroxide solution, the resulting reaction mixture was stirred at the temperature for 30 minutes to 5 hours, cooled to room temperature and then diluted with water, or steam distilled to distill the solvent. Subsequently, the remaining solution is cooled to room temperature to precipitate. The resulting precipitate is filtered off, washed with water and then dried to obtain the final desired product.

In both cases described above, high purity 2,2'-bisphenol sulfoxide was obtained in high yield of at least 95 ° C. and then light stabilizers, polyolefin modifiers, lubricant additives, pesticides or the like without further further operation. It can be used directly as these intermediates.

2,2'-bisphenol sulfide used by this invention can be manufactured by a conventional method, for example, by making a substituted phenol react with this sulfur chloride.

The present invention will be described in more detail with reference to the following examples, which are not intended to limit the scope of the present invention.

Example 1

Dissolve 6.6 g (0.02 moles) of 2,2'-bis (4-tert-butylphenol) sulfide in 30 ml of ethanol, and add 30% aqueous hydrogen peroxide solution to this solution while maintaining the temperature at 70 to 75 ° C. g (0.03 mol) was added dropwise over 20 minutes. The resulting reaction mixture was stirred at this temperature for another 1 hour, cooled to room temperature, and then 100 ml of water was added thereto to precipitate. The resulting precipitate was filtered off, washed with water and dried to obtain 6.8 g (yield 98.5%) of 2,2'-bis (4-tert-butylphenol) sulfoxide having a melting point of 150 to 152 占 폚. Next, this compound was recrystallized again in n-hexane, and the pure target of white needle crystal with melting | fusing point of 152-153 degreeC was obtained.

Elemental analysis of this compound is as follows.

Calculated Value: C 69.3%, H 7.56%, S 9.30%

Found: C 69.6%, H 7.76%, S 9.07%

EXAMPLES 2-6

The procedure of Example 1 was repeated except that 2,2'-bisphenol sulfide was used to obtain the corresponding 2,2'-bisphenol sulfoxide compounds listed in Table 1.

[Table 1]

* The values in parentheses represent the calculations.

Example 7

14.4 g (0.05 mol) of 2,2'-bis (4-chlorophenol) sulfide in a mixed solution of 20 ml of dioxane and 20 ml of water was dissolved, and the solution was kept at 60 to 65 DEG C while maintaining 30% of 8.0 g (0.07 mol) of aqueous hydrogen peroxide solution was added dropwise over 20 minutes. The resulting reaction mixture was stirred at this temperature for another 2 hours, cooled to room temperature, and then 150 ml of water was added thereto to precipitate. The resulting precipitate was filtered off, washed with water and dried to give 14.4 g (yield, 95% of theory) of 2,2'-bis (4-chlorophenol) sulfoxide having a solution of 203 to 204 캜. This compound was then recrystallized again in an ethanol aqueous solution to obtain a pure target of white acicular crystal having a melting point of 204 to 205 캜.

Elemental analysis of this compound is as follows.

Calculation: C 47.5%, H 2.66%, Cl 10.6%, S 23.4%

Found: C 47.7%, H 2.78%, Cl 10.3%, S 23.2%

Example 8

12.3 g (0.05 mol) of 2,2'-bis (4-methylphenol) sulfide was dissolved in 40 ml of carbon tetrachloride, and 8.0 g (0.07) of 30% aqueous hydrogen peroxide solution was maintained while maintaining the solution at 70 to 76 ° C. Mole) was added dropwise over 20 minutes. The resulting reaction mixture was stirred at this temperature for another 2 hours, and then steam distilled to distill carbon tetrachloride to form a precipitate. Next, the produced precipitate was filtered and dried to give 12.6 g (yield, 96.5% of theory) of 2,2'-bis (4-methylphenol) sulfoxide having a melting point of 190 to 191 ° C. This compound was then recrystallized in glacial acetic acid to obtain the pure target of white prism crystals having a melting point of 191 to 192 캜.

Elemental analysis of this compound is as follows.

Calculation: C 64.1%, H 5.37%, S 12.2%

Found: C 64.6%, H 5.40%, S 12.4%

Example 9

The procedure of Example 8 was repeated except that 2,2'-bis (4,6-dichlorophenol) sulfide was used instead of 2,2'-bis (4-methylphenol) sulfide to have a melting point of 219 to 2,2'-bis [4,6-dichlorophenol] sulfoxide (97.5% of yield theory) which is 220 degreeC was obtained. This compound was further recrystallized in ethanol to obtain the pure target of white needle crystal with melting point of 223 to 224 캜. Elemental analysis of this compound is as follows.

Calculated Value: C 38.7%, H 1.63%, Cl 38.1%, S 8.62%

Found: C 38.5%, H 1.70%, Cl 38.3%, S 8.68%

Example 10

Dissolve 4.2 g (0.1 mol) of 2,2'-bis (4-third-octylphenol) sulfide in 90 ml of benzene and maintain this solution at a temperature of 75 to 80 DEG C while adding 30% hydrogen peroxide. 17 g (0.15 mol) of an aqueous solution was added dropwise over 30 minutes. After stirring this semi-mixed liquid for 1 hour at the said temperature, and then steam distilling to distill benzene, precipitation produced. The resulting precipitate was filtered and dried to give 45.1 g (98.5% of yield theory) of 2,2'-bis (4-thi-octylphenol) sulfoxide having a melting point of 4169 to 170 ° C. This compound was further recrystallized in ethanol to obtain the pure target of colorless needle crystals with melting points of 171 to 172 캜. Elemental analysis of this compound is as follows.

Calculated Value: C 73.3%, H 9.24%, S 6.99%

Found: C 73.8%, H 93.5%, S 6.83%

Example 11

Dissolve 44..2 g (0.1 mol) of 2,2'-bis (4-thi-octylphenol) sulfide in 60 ml of benzene, and add 40 ml of water to the resulting solution at a temperature of 35 to 40 ° C. While maintaining, 17 g (0.15 mol) of 30% aqueous hydrogen peroxide solution was added dropwise over 30 minutes. Next, the reaction mixture was stirred for 4 hours at the above temperature, and then steam distilled to distill benzene to form precipitates. The precipitate thus produced was filtered and dried to give 2,2'-bis (4-thi-octylphenol) sulfoxide (yield, 98% of theory) having a melting point of 169 to 171 占 폚.

Example 12

The procedure of Example 10 was repeated except that 2,2'-bis (4-bromophenol) sulfide was used instead of 2,2'-bis (4-third-octylphenol) and the melting point was 201 to 201. 2,2'-bis (4-bromophenol) sulfoxide (yield, 96% of theory) which is 203 degreeC was obtained. When the compound was recrystallized in ethanol, a pure target of white needle crystal having a melting point of 204 to 205 캜 was obtained. Elemental analysis of this compound is as follows.

Calculation: C 36.8%, H 2.06%, Br 40.7%, S 8.17%

Found: C 37.0%, H 2.03%, Br 40.8%, S 8.21%

Example 13

Example 10 operation, except that 2,2'-bis (4-methyl-6-tertbutylphenol) sulfide was used instead of 2,2'-bis (p-tert-octylphenol) sulfide Was repeated to obtain 2,2'-bis (4-methyl-6-third-butylphenol) sulfoxide (yield, 97.5% of theory) having a melting point of 120 to 121 DEG C. The compound was recrystallized in ethanol again. Furthermore, the target compound of white needle crystal with melting point of 122-123 ° C. was obtained.

Calculated Value: C 70.5%, H 8.07%, S 8.56%

Found: C 70.4%, H 8.26%, S 8.42%

Example 14

The procedure of Example 10 was repeated except that 35.8 g (0.1 mol) of 2,2'-bis (4-thi-amylphenol) sulfide was dissolved in 70 ml of 0-chlorobenzene-melting point to 120 to 121. The yield was 96.5% of the theoretical value of 2,2'-bis (4-thi-amylphenol) sulfoxide (yield, 96.5% of theory.) The compound was recrystallized to give a colorless needle-like 2-crystal having a melting point of 122 to 124 ° C. A pure target product was obtained.The elemental analysis of this compound is as follows.

Calculated Value: C 70.5%, H 8.07%, S 8.56%

Found: C 70.6%, H 8.26%, S 8.54%

Claims (1)

The 2,2'-bisphenol sulfide of the general formula (II) is oxidized with hydrogen peroxide in the presence of an organic solvent which does not convert into an organic peracid to produce the 2,2'-bisphenol sulfoxide derivative of the general formula (I) A process for producing 2,2'-bisphenol sulfoxide characterized by the above-mentioned.

Wherein R ₁ , R ₂ and R ₃ are selected from 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 and a carboalkoxy group, and R ₁ And R ₂ · R ₂ R ₃ or R ₁ , R ₂ and R ₃ may form a ring together with carbon atoms, respectively.