SU852861A1 - Method of preparing 4-(4 -chlorophenylsulfonyl)-4'-chlorodiphenylsulfon - Google Patents

Description

The invention relates to a new method for producing 4- (4-chlorophenylsulfonyl) 4'-chlorodiphenylsulfone monomer for polycondensation polymers of the formula

D -— (θ)> ~

A known method of obtaining compounds of General formula

h. -ζδ) 2 yield of 4- (4-chlorophenylsulfonyl) -4'-chlorodiphenylsulfone. A method for producing 4- (4-chlorophenylsulfonyl) 4'-chlorodiphenylsulfone is proposed, which consists in 5 condensing the sodium salt of 4-chlorothiophenol with 4.4 ^, dichlorodiphenylsulfone at 110-140 ° C in dimethyl sulfoxide at an equimolar ratio of starting materials of 1: 1, respectively, and the subsequent oxidation of intermediate 4 (4''chlorophenylthio) -4 ^/ -chlorodiphenylsulfone.

Typically, the oxidation is carried out with hydrogen peroxide at a temperature of 100-110 ° C and a molar ratio of reactants 15, respectively 1: 3, in a solution of acetic acid according to the scheme:

50 ₂ -phC ^ - S — where R is Cl, NO ₂ , Me, H, PhSO ₂ , COOH, which consists in the condensation of the sodium salt of sulfinic acid with a nitro compound in dimethylformamide medium at 80-160 ° С. The yield is 60–70% [1].

The method is characterized by insufficiently high yield of the target product.

The aim of the invention is above ₂₀

The yield at the condensation stage is 98%, at the oxidation stage — 93–96%. The advantage of the proposed method is also the use of readily available 852861 lioro cheap raw materials obtained on an industrial scale.

Example 1. a) The synthesis of 4- (4-chloro phenylthio) -4 ^/ -chlorodiphenyl sulfone is carried out in a flask with a stirrer, reflux condenser and water separator. 7.23 g (0.05 mol) of 4-chlorothiophenol, 2.0 g (0.05 mol) of sodium hydroxide, 50 ml of dimethyl sulfoxide and 15 ml of benzene, necessary for azeotropic distillation of water, are loaded into the flask. Nitrogen is passed through the system. The mixture is heated at 130 ° C for 2 hours, cooled to 40-50 ° C and 14.32 g (0.05 mol) of 4,4 ^- dichlorodiphenyl sulfone in 50 ml of dimethyl sulfoxide are added to it. The contents are heated to 140 ° C and maintained at this temperature for 2 hours. The resulting product is cooled and poured into cold water. The precipitate formed is washed with 5% aqueous sodium hydroxide solution, water and dried. 19.36 g of the expected product are obtained. Yield 98%; t. pl. 92-95 ° C (from ethanol).

Found,%: C 54.35; H 3.28; CI 17.89.

Calculated,%: C 54.69; H 3.06; C1 17.94. b) 5.93 g (0.015 mol) of 4- (4-chlorophenylthio) -4 ^/ -chlorodiphenyl sulfone is dissolved by heating in a mixture of 30 ml of glacial 30 acetic acid and 10 ml of acetic anhydride. To the hot solution (~ 70 ° C), add 3.36 g (0.03 mol) of 30% hydrogen peroxide and the reaction mixture boiling for 4 hours. The precipitated reaction product is filtered off and dried. 5.96 g of 4- (4 ^// -chlorophenylsulfonyl) -4'-chlorodiphenylsulfone are obtained. Yield 93%: mp. 5 368—372 ° C.

Found,%: C 50,! 8; And 2.98; Ci 16.67. Calculated,% ": C 50.59; H 2.83; C1 16.59. Example 2. The experiment is carried out under the conditions of example 1, but the condensation of sodium with> 10 or 4-chlorothiophenol with 4.4 ^ζ- ΑΗχπορΑΗφεΗΗπsulfone is carried out at 110 ° C for 5 hours, followed by isolation of the product by known methods.

The output in the first stage is 96 %15

Claims (2)

Horo cheap raw materials produced on an industrial scale. Example 1. a) Synthesis of 4- (4-chloro-phenylthio) -4-chlorodiphenylsulfone is carried out in a flask with a stirrer, a cold-cooler and a water separator. 7.23 g (0.05. Mol) of 4-chlorothiophenol, 2.0 g (0.05 mol) of caustic soda, 50 ml of dimethyl sulfoxide and 15 ml of benzene, necessary for azeotropic distillation of water, are loaded into the flask. . The mixture is heated to 130 ° C irri for 2 hours, cooled to 40-50 ° C and 14.32 g (0.05 mol) of 4,4-dichlorodiphenylsulfone in 50 ml of dimethyl sulfoxide is added to it. The contents are heated to 140 ° C and kept at this temperature for 2 hours. The resulting product is cooled and poured into cold water. The precipitation is washed with 5% aqueous solution of sodium hydroxide, water and dried. 19.36 g of the expected product are obtained. Yield 98%; m.p. 92-95 ° C (from ethanol). Paideno, / “: C 54.35; And 3.28; C1 17.89. Calculated,%: C 54.69; H 3.06; C1 17.94. b) 5.93 g (0.015 mol) of 4- (4-chlorophenylthio) -4-chlorodiphenylsulfone is dissolved when heated in a mixture of 30 ml of glacial acetic acid and 10 ml of acetic anhydride. 3.36 g (0.03 mol) of 30% hydrogen peroxide is added to a hot solution (70 ° C) and the reaction mixture is boiled for 2 hours. The precipitated reaction product is filtered and dried. 5.96 g of 4- (4-chlorophenylsulfoEyl) -4-hlardiphenylsulfone are obtained. Yield 93%; m.p. 368--372 ° C. Found,%: C 50.8: H 2.98; C1 III, 67. Calculated, / o; C 50.59; P 2.83; C1 16.59. PREMI. M ER 2. The experiment was carried out under the conditions of Example 1, but the condensation of 4-chlorothiophenol sodium salt with 4,4-dichlorodiphenylsulfone was carried out at 110 ° C for 5 hours, followed by isolation of the product using known and known methods. The yield in the first stage is 96%. Formula of the invention 4-dichlorodiphenylsulfone in dimethyl sulfoxide at PO-140 ° C and an equimolar ratio of 1: 1, followed by oxidation of the resulting 4- (4-chlorophenylthio) -4-chlorodiphenylsulfone. Sources of information taken into account during the examination 1. Published for Germany No. 1806993, cl. 12o 23/30, 1970 (prototype).