GB2072161A - Bisphenol Sulfone Derivatives - Google Patents

Abstract

A process for preparing bisphenol sulfone derivatives represented by the general formula (I> <IMAGE> where R stands for hydrogen, a halogen, an alkyl radical, a cycloalkyl radical, an aryl radical, an aralkyl radical, hydroxyl group, an alkoxy radical, allyloxy group, carboxyl group, or a carboalkoxy radical, m is an integer of from 1 to 3, and when m is 2 or more, R may be identical to or different from each other, and adjacent Rs may be combined to form a ring, by oxidizing with hydrogen peroxide a compound represented by the general formula (II> <IMAGE> where R and m have the same meanings as defined for the formula (I), and n is zero or 1, in the presence of an alkali in an amount at least equal to, and preferably more than, the equimolar amount thereof relative to said compound in water and/or an organic solvent not to form any organic peracids under reaction conditions.

Description

SPECIFICATION Process for Preparing Bisphenol Sulfone Derivatives This invention relates to a novel process for preparing bisphenol sulfone derivatives.

Generally, the oxidation of sulfur compounds is effected in a glacial acetic acid solution by using solely hydrogen peroxide as oxidizing agent (peracetic acid oxidation).

The following have been known about the process in which bisphenol sulfides or bisphenol sulfoxides are oxidized to obtain the corresponding sulfones.

(1) The oxidation of sulfides with hydrogen peroxide is usually effected in glacial acetic acid (peracetic acid oxidation), but it also proceeds in an organic solvent such as acetone.

(2) The oxidation of 2,2'-bisphenol sulfides with hydrogen peroxide is effected in a similar way as above in glacial acetic acid to obtain the corresponding 2,2'- bisphenol sulfone derivatives [J. Am.

Chem. Soc., 67 238 (1966)].

(3) In a conventional process, 4,4'-diphenol sulfide is oxidized in the presence of a metallic catalyst such as molybdenum, vanadium, titanium, tungsten, or the like, in an aqueous acid solution to obtain 4,4'-diphenol sulfone. 4,4'-Diphenol sulfide is subjected to heating under reflux with a pH not more than 1 in the presence of molybdenum to obtain the final product at an yield of 99.7% (purity 97.6%) (U.S.P. 4,089,904).

(4) In the case of the preparation of bisphenol sulfone by the oxidation of bisphenol sulfoxide, the 4,4'-bisphenol sulfoxide is oxidized with hydrogen peroxide in glacial acetic acid to obtain the corresponding sulfone. For example, 4,4'-diphenol sulfoxide is subjected to oxidation at 85 OC in a large excess of glacial acetic acid to obtain the final product at an yield of 85% [L. M. Nikolenko et al, J.

General Chem. of USSR, 33, 3731 (1963)].

(5) Nothing is known about the oxidation reaction of 2,2'-bisphenoi sulfoxides. 2,2'-Bisphenol sulfoxides are only expected to form the corresponding 2,2'-bisphenol sulfone derivatives by the peracetic acid oxidation as in 4,4'-bisphenol sulfoxide mentioned above.

However, such processes as mentioned in the above items (2), (4) and (5) have many drawbacks from the standpoints of economy as well as procedures for the preparation thereof in effecting these reactions on an industrial scale, because the oxidation reaction is effected in a large excess of peracetic acid, so that the handling thereof requires to take bumpings and explosions into consideration, and because a large amount of glacial acetic acid is used and discharged into a large amount of waste water, which requires a large amount of expenditure including that for the waste liquor disposal and so forth.

The process described in the above item (3) cannot be regarded as economical and advantageous for industrial purposes due to the following reasons. In the process, a relatively expensive metallic catalyst is used, and the recovery thereof requires complicated procedures and many problems associated with environmental protections take place, because the catalyst is dissolved in the aqueous solution. Moreover, the process has such problems that the reaction conditions especially of pH remarkably affect the yield and purity of the final product, that the product is colored, and so forth.

An object of this invention is to provide a novel and industrially advantageous process for preparing bisphenol sulfone derivatives.

According to this invention there is provided a process for preparing bisphenol sulfone derivatives represented by the general formula (I)

where R stands for hydrogen, a halogen, an alkyl radical, a cycloalkyl radical, an aryl radical, an aralkyl radical, hydroxyl group, an alkoxy radical, allyloxy group, carboxyl group, or a carboalkoxy radical, m is an integer of from 1 to 3, and when m is 2 or more, R may be identical to or different from each other, and adjacent R's may be combined to form a ring; which comprises oxidizing with hydrogen peroxide a compound represented by the general formula (II)

where R and m have the same meanings as defined for the formula (I), and n is zero or 1, in the presence of an alkali in an amount of at least, and preferably more than, the equimolar amount thereof relative to said compound in a solvent selected from water and organic solvents not to form any organic peracids under reaction conditions to form said bisphenol sulfone derivatives.

In accordance with the present invention, the compounds represented by the general formula (II), that is, bisphenol sulfides (when n=O in the formula (II)) and bisphenol sulfoxides (when n=1 in the formula (II)) form the corresponding phenolates with an alkali in an amount more than the equimolar amount thereof relative to starting materials resulting a solution. The reaction of the phenolate with a theoretical amount of hydrogen peroxide causes the oxidation to proceed desirably, and after the completion of the reaction, the reaction mixture is neutralized to obtain bisphenol sulfone derivatives.

In accordance with the present invention, the phenolates of bisphenol sulfides or bisphenol sulfoxides in the formula (II) can be dissolved by the use of a small amount of such an organic solvent as not to form any organic peracids with hydrogen peroxide under reaction conditions to effect the reaction when the phenolates are insoluble in water.

Furthermore, an organic solvent instead of water can be used regardless of the solubility of the phenolate in water, which results in an extremely improved yield of the final product per volume of the reaction mixture, because a much less amount of organic solvent is sufficient compared with the amount of water used.

Alkali is required to be used in an amount at least equal to, and preferably more than, the equimolar amount thereof relative to bisphenol sulfides or bisphenol sulfoxides. No reaction proceeds in the absence of alkali.

In the case of bisphenol sulfides, the use of an alkali in an amount less than the equimolar amount thereof results in the incorporation of sulfoxides therein. The sulfone is formed in an amount proportional to the amount of alkali used, and the use of the equimolar amount of alkali causes sulfoxides to be disappeared to form sulfones entirely. On the other hand, in the case of bisphenol sulfoxides, the sulfone is formed in an amount proportional to the amount of alkali added-thereto, and the use of the equimolar amount of alkali causes to form sulfones entirely.

Examples of the alkali used in the present invention include alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like. Alkali may be used directly in the form of a solid, but generally used in the form of an aqueous solution. Alkali is usually used in an amount in the order of from the equimolar amount to 5 moles and preferably the equimolar amount to 2 moles relative to the compound of the general formula (II). However, in the case of bisphenol having carboxyl group(s) as substituent, it is necessary to add thereto alkali in an amount equivalent to the carboxyl group(s) to form a carboxylic acid alkali metal salt followed by adding thereto alkali in an amount more than the equimolar amount to form phenolates by adjusting the amount of alkali used.

The compounds represented by the general formula (II) include for example, 2,2'-bisphenol compounds represented by the general formula (III)

where R1, R2 and R3 stand for hydrogen, a halogen, an alkyl radical, a cycloalkyl radical, an aryl radical, an aralkyl radical, hydroxyl group, an alkoxy radical, allyloxy group, carboxyl group or a carboalkoxy radical, being identical to or different from each other, or R1 and R2, R2 and R3 or R1, R2 and R3 may form a ring together with the carbons of the benzene nucleus to which carbons R1, R2 and R3bond respectively, and n is zero or 1, such as 2,2'-bisphenol sulfides and 2,2'-bisphenol sulfoxides, and 4,4'bisphenol compounds represented by the general formula (IV)

where R4 and R5 have the same meanings as defined for R1 and R2 in the general formula (II), and n is zero or 1, such as 4,4'-bisphenol sulfides and 4,4'-bisphenol sulfoxides.

More specifically, examples of the above compounds include 2,2'-bisphenol sulfides such as 2,2'-diphenol sulfide, 2,2'-bis(4-methylphenol) sulfide, 2,2'-bis(6-methylphenol) sulfide, 2,2'-bis(4iso-propylphenol) sulfide, 2,2'-bis(4-n-butylphenol) sulfide, 2,2'-bis(4-sec-butylphenol) sulfide, 2,2'bis(4-tert-butylphenol) sulfide, 2,2'-bis(6-tert-butylphenol) sulfide, 2,2'-bis(4-tert-amylphenol) sulfide, 2,2'-bis(4-tert-octylphenol) sulfide, 2,2'-bis(4-nonyl-phenol) sulfide, 2,2 '-bis(4-tert-butyl-6methylphenol) sulfide, 2,2'-bis(4-methyl-6-tert-butylphenol) sulfide, 2,2'-bis(4,6-dimethylphenol) sulfide, 2,2'-bis(4,6-di-tert-butylphenoi) sulfide, 2,2'-bis(4,5-dimethylphenol) sulfide, 2,2'-bis(4cyclohexylphenol) sulfide, 2,2'-bis(4-cyclohexyl-6-methylphenol) sulfide, 2,2'-bis(4,6-dicyclohexyl- phenol) sulfide, 2,2'-bis(4-a,a'-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-a,a'-dimethylbenzyl-6-phenyl-phenol) 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(4,6dimethoxyphenol) sulfide, 2,2'-bis(4-carboxyphenol) sulfide, 2,2'-bis(4-carbomethoxyphenol) sulfide, 2,2'-bis(4-carbobutoxyphenol) sulfide, 1,1 '-bis(2-naphthol) sulfide, 2,2'-bis( 1 -naphthol) sulfide and the like, 2,2'-bisphenol sulfoxides such as 2,2'-diphenol sulfoxides, 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) sulfide, 2,2'-bis(4-sec-butylphenol) sulfoxide, 2,2'-bis(4-tert-butylphenol) sulfoxide, 2,2'-bis(6-tertbutylphenol) sulfoxide, 2,2'-bis(4-tert-amylphenol) sulfoxide, 2,2'-bis(4-tert-octylphenol) sulfoxide, 2,2'-bis(4-nonylphenol) sulfoxide, 2,2'-bis(4-tert-butyl-6-methylphenol) sulfoxide, 2,2'-bis(4-methyl6-tert-butylphenol) sulfoxide, 2,2'-bis(4,6-dimethylphenol) sulfoxide, 2,2'-bis(4,6-di-tert-butylphenol) sulfoxide, 2,2'-bis(4,5-dimethylphenol) sulfoxide, 2,2'-bis(4-cyclohexylphenol) sulfoxide, 2,2'-bis(4cyclohexyl-6-methylphenol) sulfoxide, 2,2'-bis(4,6-dicyclohexylphenol) sulfoxide, 2,2'-bis(4-,i',a'- dimethyl-benzylphenol) sulfoxide, 2,2'-bis(4-benzylphenol) sulfoxide, 2,2'-bis(4,6-dibenzylphenol) sulfoxide, 2,2'-bis(4-phenylphenol) sulfoxide, 2,2'-bis(4-phenyl-6-methylphenol) sulfoxide, 2,2'-bis(4 a,a'-dimethylbenzyl-6-phenylphenol) sulfoxide, 2,2'-bis(4-chlorophenol) sulfoxide, 2,2'-bis(4,6dichlorophenol) 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(4,6dimethylphenol) sulfoxide, 2,2'-bis(4-carboxyphenol) sulfide, 2,2'-bis(4-carbomethoxyphenol) sulfoxide, 2,2'-bis(4-carbobutoxyphenol) sulfoxide, 1,1 '-bis(2-naphthol) sulfoxide, 2,2'-bis( 1 -naphthol) sulfoxide and the like, 4,4'-bisphenol sulfides such as 4,4'-diphenol sulfide, 4,4'-bis(2-chlorophenol) sulfide, 4,4'-bis(3-chlorophenol) sulfide, 4,4'-bis(2-methylphenol) sulfide, 4,4'-bis(3-methylphenol) sulfide, 4,4'-bis(2,5-dimethylphenol) sulfide, 4,4'-bis(2-isopropyl-5-methylphenol) sulfide, 4,4'-bis(2methyl-6-tert-butylphenol) sulfide, 4,4'-bis(2,6-dj-tert-butylphenol) sulfide, 4,4'-bis(2-hydroxyphenol) sulfide, 4,4'-bis(2-carboxyphenol) sulfide, 4,4'-bis(2-carbomethoxyphenol) sulfide and the like, and 4,4'-bisphenol sulfoxides such as 4,4'-diphenol sulfoxide, 4,4'-bis(2,5-dimethylphenol) sulfoxide, 4,4'bis(2-tert-butyl-phenol) sulfoxide, 4,4,-bis(2-cyclohexylphenol) sulfide, 4,4'-bis(2-tert-butyl-5methylphenol) 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-carbomethoxyphenol) sulfoxide and the like.

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

The organic solvents used in the process of the present invention include any conventional organic solvents excluding any organic acids which form organic peracids with hydrogen peroxide under the reaction conditions, and more specifically includes aliphatic, alicyclic and aromatic hydrocarbons such as hexane, cyclohexane, heptane, benzene, toluene, xylene and ethyl benzene; aliphatic, alicyclic and aromatic halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, chlorobenzene and o-dichlorobenzene; alcohols such as methanol, ethanol, propanol and butanol; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane; ketones such as acetone and methylethylketone; esters such as acetic acid esters and propionic acid esters, aprotic polar solvents such as N,N-dimethylformamide, dimethylsulfoxide, and N-methyl pyrrolidone, carbon disulfide, and the like.

The above solvents may be used as a mixture thereof, or as a mixture thereof with water.

The use of hydrocarbon and halogenated hydrocarbon solvents immiscible with water specifically such as benzene, toluene, xylene, chlorobenzene, dichloroethane and carbon tetrachloride among the solvents mentioned above, enables the solvents to be recovered by steam distillation after completion of the reaction. The recovered solvents can be directly reused by circulation, or, if required, can be further subjected to a purification treatment such as distillation for reuse, which results in not only serving the reduction of the amounts of the solvents used leading to reducing the cost, but also decreasing the problems associated with environmental protections with great industrial advantages.

The solvent is generally used in an amount of from 0.5 to 10 parts by volume and preferably from about 2 to 5 part by volume per one part by weight of the sulfide as starting material.

Hydrogen peroxide is used as an aqueous hydrogen peroxide at various concentrations, and preferably as an aqueous hydrogen peroxide at a concentration in the range of from 30 to 35% due to an easiness in its handling. Hydrogen peroxide is usually used in a little excess over the amount theoretically required relative to bisphenols, but may also be used in an amount in the range of from 1.5 to 5.0 times the amount theoretically required. Hydrogen peroxide is added either drop by drop to an alkaline solution of said sulfoxide, or mixed with the solution in advance.

The reaction of the present invention is usually carried out at a temperature of from 30 to 11000.

If the reaction temperature is lower than 300C, the reaction requires a long period of time, while if the reaction temperature is higher than 11000, the concentration of hydrogen peroxide is extremely reduced, and unfavorable phenomena such as bubbling take place, which results in preventing the reaction from taking place. The reaction temperature is more preferably of from 50 to 1 000 C. In the practice of the process of the present invention, generally a bisphenol and an equimolar amount of alkali are dissolved in water and/or an organic solvent. While this solution is kept at a temperature of 300--1 1000, an aqueous hydrogen peroxide is added thereto drop by drop. After the addition by dropping of the aqueous hydrogen peroxide is completed, the resulting reaction mixture is stirred at that temperature for additional 30 minutes to 5 hours. After the reaction mixture is allowed to cool to room temperature, a precipitate is formed by neutralizing the reaction mixture directly with acid, by diluting it with water or subjecting it to steam distillation to distill off the solvent after neutralization, or by subjecting the reaction mixture to steam distillation directly as an alkali solution followed by neutralizing it. The precipitate is separated by filtration, washed with water, and dried to obtain bisphenol sulfone derivatives as the final product.

In any cases mentioned above, bisphenol sulfone derivatives can be obtained at a high yield of 95% or above as a product of such a high purity as to be directly used without being subjected to additional procedures specifically as light stabilizers, polyolefin modifiers, lubricant additives, agricultural chemicals, or intermediates thereof.

Bisphenol sulfoxides used in the present invention can be prepared according to known processes, for example, by reacting a substituted phenol with thionyl chloride in the presence of anhydrous aluminum chloride.

In accordance with the present invention, the use of a theoretical amount of hydrogen peroxide causes the reaction to proceed desirably, and even the use of a large excess of hydrogen peroxide causes no problems. Moreover, according to the process of the present invention, no formation of any oxidation by-products is recognized and the corresponding bisphenol sulfone derivatives of extremely high purity can be obtained at an approximateiy quantitative yield, which results in great industrial advantages.

The process of the present invention is further illustrated by the following examples.

Example 1 In a solution of 6 g (0.15 mole) ot sodium hydroxide and 100 ml of water was dissolved 24.6 g (0.1 mole) of 2,2'-bis(4-methylphenol) sulfide. While this solution was kept at a temperature of 70 750C, 28.3 g (0.25 mole) of 30% aqueous hydrogen peroxide solution was added thereto drop by drop over a period of 30 minutes. The resulting reaction mixture was stirred at that temperature for an additional hour, and then diluted with 100 ml of water. The resulting solution was allowed to cool to room temperature and then was neutralized to form a precipitate.The precipitate was separated by filtration, washed with water, and dried to obtain an yield of 26.8 g (96.4% of theory) of 2,2'-bis(4methylphenol) sulfone having a melting point of 205--2060C. The precipitate was further subjected to recrystallization from glacial acetic acid to obtain a pure product melting at a temperature of 2072080C as white needle-like crystals.

The results of elemental analysis were as follows: C(%) H{%) S{%) Calculated Values 60.4 5.07 11.5 FoundValues 60.7 5.12 11.7 Example 2 In a solution of 5 g (0.125 mole) of sodium hydroxide and 100 ml of water was dissolved 26.2 g (0.1 mole) of 2,2'-bis(4-methylphenol) sulfoxide. While this solution was kept at a temperature of 70 750C, 17 g (0.15 mole) of 30% hydrogen peroxide solution was added thereto drop by drop over a period of 30 minutes. The resulting reaction mixture was stirred at that temperature for an additional hour, and then diluted with 100 ml of water. The resulting solution was allowed to cool to room temperature and then was neutralized to form a precipitate.The precipitate was separated by filtration, wash with water, and dried to obtain an yield of 27.1 g (97.5% of theory) of 2,2'-bis(4-methylphenol) sulfone having a melting point of 205-2060C.

Example 3 In 40 ml of ethanol was 28.7 g (0.1 mole) of 2,2'-bis(4-chlorophenol) sulfide. To the resulting solution was added 20 g (0.15 mole) of 30% aqueous sodium hydroxide solution, and then 28.3 g (0.25 mole) of 30% aqueous hydrogen peroxide solution was added thereto drop by drop over a period of 30 minutes, while the solution was kept at a temperature of 65--700C. The resulting reaction mixture was stirred at that temperature for an additional hour, and then diluted with 50 ml of water.

The resulting solution was allowed to cool to room temperature and then was neutralized to form a precipitate. The precipitate was separated by filtration, washed with water, and dried to obtain an yield of 30.9 g (97% of theory) of 2,2'-bis(4-chlorophenol) sulfone having a melting point of 189-1 90cm.

The precipitate was further subjected to recrystallization from glacial acetic acid to obtain a pure product melting at a temperature of 191-1 920C as white needle-like crystals.

The results of elemental analysis were as follows: C(%) H{%) Cuff%) S{%) Calculated Values 45.2 2.52 22.2 10.0 Found Values 45.6 2.48 22.5 10.5 Examples F9 The procedure of Example 3 was repeated except that 2,2'-bisphenol sulfides were used to obtain the corresponding 2,2'-bisphenol sulfones with the results as shown in Table I.

Table 1 Values byElementalAnalysis (%) Example 2,2'-bisphenol sulfone Yield(%) m.p. (0C) C H S Br 4 2,2'-diphenolsulfone 98 190-191 57.3 4.11 12.4 (57.6) (4.03) (12.8) 5 2,2'-bis(4-bromophenol) 95.5 209-210 35.7 1.95 7.79 39.5 sulfone (35.3) (1.97) (7.85) (39.2) 6 2,2'-bis(4-cyclohexyl 97.0 177-179 69.9 7.33 7.81 phenol) sulfone (69.5) (7.29) (7.73) 7 2,2'-bis(4-a, r'-dimethyl- 98.0 139-140 74.2 6.38 6.34 benzylphenol) sulfone (74.1) (6.21) (6.59) 8 2,2'-bis(4-phenylphenol) 95.0 221-222 71.9 4.63 7.91 sulfone (71.6) (4.51) (7.97) 9 1,1'-bis(2-naphthol) 95.0 235 68.0 4.03 9.19 sulfone (decompo- (68.6) (4.03) (9.15) sition) *Values in brackets show calculated values.

Example 10 In 50 ml of 1,2-dichloroethane was dissolved 33 g (0.1 mole) of 2,2'-bis(4-tert-butylphenol) sulfide. To this solution was added 20 g (0.15 mole) of 30% sodium hydroxide aqueous solution, and then 28.3 g (0.25 mole) of 30% aqueous hydrogen peroxide was added thereto drop by drop over a period of 30 minutes, while the solution was kept at a temperature of 45-500C. The resulting reaction mixture was stirred at that temperature for additional three hours, and then was neutralized.

Then, the reaction mixture was subjected to steam distillation to distill off 1,2-dichloroethane, forming a precipitate. After being allowed to cool to room temperature, the precipitate was separated by filtration, washed with water, and dried to obtain 35.5 g (98% of theory) of 2,2'-bis(4-tert-butylphenol) sulfone having a melting point of 1 29-1 300C. The precipitate was subjected to recrystallization from n-hexane to obtain a pure product melting at a temperature of 131-1 32.50C as white needle-like crystals.

The results of elemental analysis were as follows: C(%) H(%) S(%) Calculated Values 66.3 7.23 8.85 Found Values 66.1 7.50 8.66 Example 11 The procedure of Example 10 was repeated except that 2,2'-bis(4,6-dichlorophenol) sulfide was used to obtain 2,2'-bis(4,6-dichlorophenol) sulfone having a melting point of 1 68-1 700C at an yield of 96%.

The thus-obtained product was subjected to recrystallization from ethanol to obtain a pure product melting at a temperature of 170-171 C as white needle-like crystals.

The results of elemental analysis were as follows: C(%) H{%) Cl(%) S{%) Calculated Values 37.1 1.56 36.5 8.26 Found Values 37.4 1.61 36.6 8.42 Example 12 A mixture of 44.2 g (0.1 mole) of 2,2'-bis(4-tert-octylphenol) sulfide, 30 g (0.15 mole) of 20% aqueous sodium hydroxide solution, 28.3 g (0.25 mole) of 30% aqueous hydrogen peroxide solution and 60 ml of benzene was stirred at a temperature of 70-750C for 3 hours, and then was subjected to steam distillation to distill off benzene. The resulting reaction mixture was neutralized to form a precipitate. After being allowed to cool to room temperature, the precipitate was separated by filtration, washed with water, and dried to obtain 46.6 g (98.5% of theory) of 2,2'-bis(4-tert octylphenol) sulfone having a melting point of 1 42--1 43 OC.

The above product was further subjected to recrystallization from glacial acetic acid to obtain a pure product melting at a temperature of 143-1 450C as white needle-like crystals.

The results of elemental analysis were as follows: C{%) H(%) S{%) Calculated Values 70.9 8.92 6.75 Found Values 70.7 8.78 6.77 Example 13 The procedure of Example 1 2 was repeated except that 2,2'-bis(4-methyl-6-tert-butylphenol) sulfide was used to obtain 2,2'-bis(4-methyl-6-tert-butylphenol) sulfone having a melting point of 130-131 OC at an yield of 95.5%.

The above product was subjected to recrystallization from ethanol to obtain a pure product melting at a temperature of 1 32-1 340C as white needle-like crystals.

The results of elemental analysis were follows: Ack%) H{%) S(%) Calculated Values 67.6 7.74 8.21 Found Values 67.7 7.82 8.01 Example 14 In 30 ml of chiorobenzene was dissolved 35.8 g (0.1 mole) of 2,2'-bis(4-tert-amylphenol) sulfide.

To this solution was added 36.5 g (0.13 mole) of 20% aqueous potassium hydroxide solution. To the resulting solution was added drop by drop 28.3 g (0.25 mole) of 30% aqueous hydrogen peroxide solution over a period of 30 minutes, while the solution was kept at a temperature of 75-800C. The resulting reaction mixture was stirred at that temperature for an additional hour followed by neutralization. The reaction mixture was subjected to steam distillation to distill off chlorobenzene, forming a precipitate. After being allowed to cool to room temperature, the precipitate was separated by filtration, washed with water, and dried to obtain an yield of 37.6 g (96.5% of theory) of 2,2'-bis(4 tert-amylphenol) sulfone having a melting point of 11 7-11 80C.

The above product was subjected to recrystailization from n-hexane to obtain a pure product melting at a temperature of 1 19--1200C as white prism-iike crystals.

The results of elemental analysis are as follows: C{%} %) S(%) Calculated Values 67.6 7.74 8.21 Found Values 67.4 7.82 8.08 Example 15 In 40 ml of ethanol was dissolved 29.3 g (0.1 mole) of 2,2'-bis(4-chlorophenol). To this solution was added 20 g (0.15 mole) of 30% aqueous sodium hydroxide solution, and then 17 g (0.15 mole) of 30% aqueous hydrogen peroxide solution was added thereto drop by drop over a period of 30 minutes, while the solution was kept at a temperature of 65-700C. The resulting reaction mixture was stirred at that temperature for an additional hour, and then diluted with 50 ml of water. After being allowed to cool to room temperature, the reaction mixture was neutralized to form a precipitate.The precipitate was separated by filtration, washed with water, and dried to obtain 31.2 g (98% of theory) of 2,2'bis(4-chlorophenol) sulfone having a melting point of 190-191 OC.

Example 16 The procedure of Example 1 5 was repeated except that 2,2'-bis(4-bromophenol) sulfoxide was used to obtain 2.2'-bis(4-bromophenol) sulfone melting at a temperature of 207--208cC at an yield of 97%.

Example 17 In 50 ml of 1 2-dichloroethane was dissolved 34.6 g (0.1 mole) of 2,2'-bis(4-tert-butylphenol) sulfoxide. To this solution was added 20 g (0.1 5 mole) of aqueous sodium hydroxide solution, and then 1 7 g (0.1 5 mole) of 30% aqueous hydrogen peroxide solution was added thereto drop by drop over a period of 30 minutes, while the solution was kept at a temperature of 45--500C. The resulting reaction mixture was stirred at that temperature for additional three hours followed by neutralization.

The reaction mixture was further subjected to steam distillation to form a precipitate. After being allowed to cool to room temperature, the precipitate was separated by filtration, washed with water, and dried to obtain 35.6 g (98.5% of theory) of 2,2'-bis(4-tert-butylphenol) sulfone having a melting point of 130-1 320C.

Example 18 The procedure of Example 1 7 was repeated except that 2,2'-bis(4,6-dichlorophenol) sulfoxide was used to obtain 2,2'-bis(4,6-dichlorophenol) sulfone having a melting point of 1 69-1 700C at an yield of 97.5%.

Example 19 A mixture of 45.8 g (0.1 mole) of 2,2t-bis(4-tert-actylphenol) sulfoxide, 30 g (0.1 5 mole) of 20% aqueous sodium hydroxide solution, 17 g (0.15 mole) of 30% aqueous hydrogen peroxide solution, and 60 ml of benzene was stirred at a temperature of 70--7 5 OC for 3 hours, and then the resulting reaction mixture was subjected to steam distillation to distill off benzene. The reaction mixture was neutralized to form a precipitate. After being allowed to cool to room temperature, the precipitate was separated by filtration, washed with water, and dried to obtain an yield of 46.9 g (99% of theory) of 2,2'-bis(4-tert-octylphenol) sulfone having a melting point of 1 42--1 43 OC.

Example 20 The procedure of Example 1 9 was repeated except that 2,2'-bis(4-methyl-6-tert-butylphenol) sulfoxide to obtain 2,2'-bis(4-methyl-6-tert-butylphenol) sulfone having a melting point of 1 30- 1310C.

Example 21 In 30 ml of chlorobenzene was dissolved 37.4 g (0.1 mole) of 2,2'-bis(4-tert-amylphenol) sulfoxide. To this solution was added 36.5 g (0.13 mole) of 20% aqueous potassium hydroxide solution. and then 17 g (0.15 mole) of 30% aqueous hydrogen peroxide solution was added thereto drop by drop over a period of 30 minutes, while the solution was kept at a temperature of 75-800C.

The resulting reaction mixture was stirred at that temperature for an additional hour followed by neutralization. The reaction mixture was further subjected to steam distillation to distill off chlorobenzene, forming a precipitate. After being allowed to cool to room temperature, the precipitate was separated by filtration, washed with water, and dried to obtain 38 g (97.5% of theory) of 2,2'bis(4-tert-amylphenol) sulfone having a melting point of 1 1 7--1 1 8 OC.

Example 22 In a solution of 5 g (0.125 mole) of sodium hydroxide and 100 ml of water was dissolved 21.8 g (0.1 mole) of 4,4'-bisphenol sulfide. To this solution was added drop by drop 28.3 g (0.25 mole) of 30% aqueous hydrogen solution peroxide over a period of 30 minutes, while the solution was kept at a temperature of from 60-650C. The resulting reaction mixture was stirred at that temperature for additional two hours. After being allowed to cool to room temperature, the reaction mixture was neutralized to form a precipitate. The precipitate was separated by filtration, washed with a cold water, and dried to obtain 23.5 g (94% of theory) of 4,4'-diphenol sulfone having a melting point of 245 246"C.

The above product was subjected to recrystallization from water to obtain a pure product having a melting point of 247-2480C as white needle-like crystals.

Examples 23-25 The procedure of Example 22 was repeated except that 4,4'-bisphenol sulfides were used to obtain the corresponding sulfones with the results as shown below.

Example Final Product Yield f /O) m.p. (OCI 23 4,4'-bis(2-methylphenol) sulfone 95.5 27=271 24 4,4'-bis(3-methylphenoi) sulfone 95 205-206 25 4,4'-bis(3-chlorophenol) sulfone 97 219-220 Example 26 In 80 ml of ethanol was dissolved 27.7 g (0.1 mole) of 4,4'-bis(2-chlorophenol) sulfide. To this solution was added a solution obtained by dissolving 5 g (0.125 mole) of sodium hydroxide in 20 ml of water.To the resulting solution was added drop by drop 28.3 g (0.25 mole) of 30% aqueous hydrogen peroxide solution over a period of 30 minutes, while the solution was kept at a temperature of 70 75 OC. The resulting reaction mixture was stirred at that temperature for additional two hours. After being allowed to cool to room temperature, the reaction mixture was neutralized to form a precipitate.

The precipitate was separated by filtration, washed with water, and dried to obtain 29.0 g (94% of theory) of 4,4'-bis(2-chlorophenol) sulfone having a melting point of 195-1 970C.

The above product was further subjected to recrystallization from a mixture of ethanol and water to obtain a pure product having a melting point of 196-1 970C as white needle-like crystals.

Examples 27-28 The procedure of Example 26 was repeated except that 4,4'-bisphenol sulfides were used as starting materials to obtain the corresponding sulfones with the results as shown below.

Example FinalProduct Yield { /O) m.p. (0C) 27 4,4'-bis(2,5-dimethylphenol) sulfone 96 256-257 28 4,4'-bis(2-isopropyl-5-methylphenol) 95 218-220 sulfone Example 29 In a solution of 7.0 g (0.125 mole) of potassium hydroxide and 100 ml of water was dissolved 23.4 g (0.1 mole) of 4,4'-diphenol sulfoxide. To this solution was added drop by drop 14.2 g (0.125 mole) of 30% aqueous hydrogen peroxide solution over a period of 30 minutes, while the solution was kept at a temperature of 55-600C. The resulting reaction mixture was stirred at that temperature for additional three hours. After being allowed to cool to room temperature, the reaction mixture was neutralized to form a precipitate.The precipitate was separated by filtration, washed with a cold water, and dried to obtain 23.9 g (96% of theory) of 4,4'-diphenol sulfone.

Example 30 In 150 ml of xylene was dissolved 37.4 g (0.1 mole) of 4,4'-bis(2-tert-butyl-5-methylphenol) sulfoxide. To this solution was added 36.5 g (0.13 mole) of 20% aqueous potassium hydroxide solution, and then 14.2 g (0.125 mole) of 30% aqueous hydrogen peroxide solution was added thereto drop by drop over a period of 30 minutes, while the solution was kept at a temperature of 75-800C.

The resulting reaction mixture was stirred at that temperature for additional two hours followed by neutralization.

The reaction mixture was further subjected to steam distillation to distill off xylene, forming a precipitate. After being allowed to cool to room temperature, the precipitate was separated by filtration, washed with water, and dried to obtain 38.0 g (98% of theory) of 4,4'-bis(2-tert-butyl-5methylphenol) sulfone having a melting point of 248--2500C. The above product was further subjected to recrystallization from ethanol to obtain a pure product having a melting point of 250251 0C as white needle-like crystals.

Examples 31-32 The procedure of Example 30 was repeated except that 4,4'diphenol sulfoxide were used as starting materials to obtain the corresponding sulfones with the results as shown below.

Example Final Product Yield (O/ol m.p. { C) 31 4,4'-bis(2-phenylphenol) sulfone 97 247-248 32 4,4'-bis(2-carbomethoxyphenol) sulfone 95 204-205 Example 33 In a solution of 13.2 g (0.33 mole) of sodium hydroxide and 150 ml of water was dissolved 32.2 g (0.1 mole) of 4,4'-bis(2-carboxyphenol) sulfoxide. To this solution was added drop by drop 14.2 g (0.125 mole) of 30% aqueous hydrogen peroxide solution over a period of 30 minutes, while the solution was kept at a temperature of 50-600C. The resulting reaction mixture was stirred at that temperature for additional four hours. After being allowed to cool to room temperature, the reaction mixture was neutralized to form a precipitate. The precipitate was separated by filtration, washed with water, and dried to obtain 33 g (97.5% of theory) of 4,4'-bis(2-carboxyphenol) sulfone having a melting point of 301-3030C.

The above product was further subjected to recrystallization from a mixture of acetic acid and water to obtain a pure product having a melting point of 303-3040C as white needle-like crystals.

Claims (11)

Claims

1. A process for preparing bisphenol sulfone derivatives represented by the general formula (I)

where R stands for hydrogen, a halogen, an alkyl radical, a cycloalkyl radical, an aryl radical, an aralkyl radical, hydroxyl group, an alkoxy radical, allyloxy group, carboxyl group, or a carboalkoxy radical, m is an integer of from 1 to 3, and when m is 2 or more, R may be identical to or different from each other, and adjacent R's may be combined to form a ring; which comprises oxidizing with hydrogen peroxide a compound represented by the general formula (II)

where R and m have the same meanings as defined for the formula (I), and n is zero or 1, in the presence of an alkali in an amount of at least the equimolar amount thereof relative to said compound in a solvent selected from water and organic solvents not to form any organic peracids under reaction conditions to form said bisphenol sulfone derivatives.

2. A process according to Claim 1, wherein the compounds of the general formula (II) are 2,2'bisphenol sulfides and 2,2'-bisphenol sulfoxides represented by the general formula (III)

where R1, R2 and R3 stand for hydrogen, a halogen, an alkyl radical, a cycloalkyl radical, an aryl radical, an aralkyl radical hydroxyl group, an alkoxy radical, allyloxy group, carboxyl group or a carboalkoxy radical, being identical to or different from each other, or R, and R2, R2 and R3 or R1, R2 and R3 may form a ring with the carbons of the benzene nucleus to which carbons R" R2 and R3 bond respectively, and n is zero or 1.

3. A process according to Claim 1, wherein the compounds of the general formula (II) are 4,4'bisphenol sulfides and 4,4'-bisphenol sulfoxides represented by the general formula (IV)

where R4 and R6 have the same meanings as defined for R1 and R2 in the general formula (III), and n is zero or 1.

4. A process according to any one of claims 1, 2 and 3 wherein said organic solvent is selected from aliphatic, alicyclic and aromatic hydrocarbons, halogenated aliphatic, alicyclic and aromatic hydrocarbons, alcohols, esters, ketones, aprotic polar solvents, or carbon disulfide.

5. A process according to any one of claims 1, 2 and 3 wherein a hydrocarbon or halogenated hydrocarbon immiscible with water is used as said solvent, the reaction mixture is neutralized after the completion of reaction, the solvent is recovered by steam distillation, and the final product is obtained as a precipitate.

6. A process according to Claim 5, wherein the hydrocarbon or halogenated hydrocarbon immiscible with water is benzene, toluene, xylene, chlorobenzene, dichloroethane or carbon tetrachloride.

7. A process according to any one of claims 1, 2 and 3 wherein the reaction is effected in an aqueous medium.

8. A process according to any one of the preceding claims wherein the amount of said hydrogen peroxide is of from a theoretical amount thereof to 5.0 times the theoretical amount thereof relative to the compound of the general formula (11).

9. A process according to any one of the preceding claims, wherein the amount of alkali is of from 1 to 5 moles per mole of the compound of the general formula (III).

10. A process according to any one of the preceding claims, wherein said alkali is an alkali metal hydroxide.

11. A process according to any one of the preceding claims wherein the reaction temperature is in the range of from 30 to 1 100C.

1 2. A process for preparing bisphenol sulfone derivatives, substantially as described herein.