RU2131870C1 - Method of preparing halogen- and/or alkyl substituted diaryl-sulfones - Google Patents

Abstract

FIELD: chemistry of polymers, more particularly manufacture of thermostable polymeric materials, semiproducts for synthesis of dyes, tanning agents and pharmaceutical materials. SUBSTANCE: method comprises reacting aromatic hydrocarbons with arenesulfonyl chlorides in the presence of heterogeneous alumooxide catalyst containing 1.2 wt % of silicon oxide. Catalyst is used in amount of 10-3 wt % based on reaction mixture weight. Reaction is carried out at 140-180 C and aromatic hydrocarbon to arenesulfonyl chloride molar ratio of 2: 10: 1. EFFECT: smaller amount of acid waste, simplified isolation and purification of the desired products, and improved quality of sulfones. 5 ex

Description

 The invention relates to an improved method for producing halogen and / or alkyl substituted diaryl sulfones.

 These compounds are used as monomers and intermediates for the preparation of heat-resistant polymer materials, intermediates for the synthesis of dyes, tannins and pharmaceutical materials.

Known methods for producing diaryl sulfones by the action of arenesulfonic acids on aromatic hydrocarbons. Arensulfonic acids in this process are often obtained in situ by the action of various sulfonating agents on aromatic hydrocarbons. The water liberated in the reaction is distilled off in the form of an azeotropic mixture, or is bound by some chemical method. To obtain 4,4'-dichlorodiphenyl sulfone by this method, strong sulfonating agents are used: chlorosulfonic acid, oleum, liquid sulfuric anhydride and fluorosulfonic acid, and phosphorus pentaoxide, phosphorus pentachloride and phosphorus trichloride, phosphorus oxychloride, thionyl chloride are used as water-absorbing agents. The reaction is carried out at 150-200 ^o C, the product yield reaches 65% [US Pat. U.S. N 3579590, 12.12.67; Pat. Japan N 24662, 05.27.66; Japanese Application N 56-131561, 03.03.80]. The disadvantage of these methods is the presence of a highly corrosive environment, the formation of significant amounts of acidic waste.

Another method for producing sulfones is a method based on the Friedel-Crafts reaction. According to this method, aromatic hydrocarbons are sulfonylated by arenesulfonyl chlorides in the presence of Friedel-Crafts catalysts (AlCl ₃ , FeCl ₃ , etc.). The reaction is carried out at 0-140 ^o C in a solution of sulfonylated compounds or in such solvents as nitrobenzene, nitromethane, methylene chloride and others. [Suter C. Chemistry of organic sulfur compounds. - M.: Publishing. in. lit., 1951. - Ch. 1-3; Olah GA, Kobayaski S., Nishimura J / J. Am. Chem. Soc. - 1973. - Vol. 95. N 2. - P. 564-569; Jensen FR, Goldman G. Sulfonylation // Friedel-Crafts and related reactions. - NY - L. - Sydney: Academic Press, 1964. - Vol. 2. - P. 1319-1347]. There is a report on the use as catalyst in the sulfonylation reaction of chlorobenzene 4-chlorobenzenesulfonyl chloride FeCl ₃ [US Pat. USA N 3334146, 08.19.74]. The reaction is carried out at 90 ^o C, a molar ratio of chlorobenzene: 4-chlorobenzenesulfonyl chloride 1: 1.2, in the presence of 1 wt.% FeCl ₃ . To wash off the catalyst, the reaction mass is washed with HCl until a negative reaction for iron ions at 70-90 ^o C to prevent crystallization. Then the reaction mass is cooled, the precipitated crystals of 4,4'-dichlorodiphenylsulfone are separated from the mother liquor. For purification from isomers, the product is crystallized from chlorobenzene. The yield of 4,4'-dichlorodiphenyl sulfone is 86%. When FeCl _{3 is} used as a catalyst, complexes are formed with the starting sulfonyl chloride and the resulting sulfone, but these complexes are less durable than complexes with AlCl ₃ and decompose under reaction conditions with catalyst regeneration; therefore, FeCl ₃ can be used in catalytic amounts (1-3 %).

Closest to the proposed is a method of producing sulfone by the interaction of 4-methylbenzenesulfonyl chloride with xylene in the presence of AlCl ₃ [US Pat. US N 2781402, 12/02/57]. The reaction is carried out at 45-60 ^o C, an excess of xylene is used as a solvent. Sulfonyl chloride reacts with an aromatic hydrocarbon only as a complex with a catalyst. The resulting sulfone also forms a complex with the catalyst. Therefore, in this method, at least 1 mol of catalyst per 1 mol of sulfonyl chloride is used. For the decomposition of catalytic complexes and washing from the catalyst, the reaction mass is washed with hydrochloric acid, water, 10% NaOH and 15% NaCl. To remove traces of catalyst, the sulfone is distilled. The yield of 4.3'4'-trimethyldiphenyl sulfone by this method is 92%.

 Although the methods based on the Friedel-Crafts reaction make it possible to obtain sulfones with high yields (up to 95%), the process often forms a difficult to separate mixture of isomers. not regenerated.

 The objective of the invention is to reduce the amount of acidic waste, simplifying the isolation and purification of target products, improving the quality of sulfones.

A method for producing halogen and / or alkyl substituted diaryl sulfones by reacting the corresponding aromatic hydrocarbons and arenesulfonyl chlorides in the presence of a heterogeneous alumina catalyst containing 1-2 wt.% Silicon oxide is proposed. The catalyst is used in an amount of 10-30 wt.% Of the reaction mass. The process is carried out at 140-180 ^o C and the ratio of aromatic hydrocarbon: arenesulfonyl chloride 2-10: 1.

The specified catalyst is obtained by treating alumina with tetraethoxysilane and then nitric acid, followed by calcination at 550 ^° C. This gives a catalyst with a particle size of 0.1-0.5 mm.

 The interaction of aromatic hydrocarbon and arenesulfonyl chloride is carried out in a batch reactor, the reaction time is 16-22 hours

 The difference of the proposed method from the prototype is the use of a new catalyst with the specified process parameters. The catalyst, being heterogeneous, can be used repeatedly. In addition, the process significantly reduces the amount of acidic waste, simplifies the selection and purification of target products.

Example 1. 4.8 g (20 wt.%) Of an Alumina catalyst containing 1.2 wt. % silica, 20 g (0.18 mol) of chlorobenzene and 3.8 g (0.018 mol) of 4-chlorobenzenesulfonyl chloride (molar ratio of chlorobenzene: 4-chlorobenzenesulfonyl chloride 10: 1) are loaded into the reactor. With constant stirring, the temperature of the reaction mixture was raised to 180 ^° C. and the mixture was kept at this temperature for 21 hours. Then the reaction mass was discharged from the reactor, the catalyst was separated off, and excess chlorobenzene was distilled off. The obtained 4,4'-dichlorodiphenylsulfone is recrystallized from acetic acid. Yield 65%, T _mp = 149-152 ^o C.

Example 2. 4 g (10 wt.%) Of an Alumina catalyst containing 1.0 wt. % silica, 20 g (0.19 mol) of 1,4-dimethylbenzene and 19.9 g (0.09 mol) of 4-chlorobenzenesulfonyl chloride (molar ratio of 1.4-dimethylbenzene: 4-chlorobenzenesulfonyl chloride 2: 1) are loaded into the reactor. The temperature of the reaction mixture with constant stirring was raised to 160 ^o C and the mixture was kept at this temperature for 16 hours. The reaction mixture was treated analogously to example 1. Yield of 4-chloro-2 ', 5'-dimethyldiphenyl sulfone 65%, T _mp = 129-132 ^o C.

Example 3. 2.7 g (10 wt.%) Of an Alumina catalyst containing 2.0 wt. % silica, 20 g (0.017 mol) of 1,3,5-trimethylbenzene, 7 g (0.003 mol) of 4-chlorobenzenesulfonyl chloride (molar ratio of 1,3,5-trimethylbenzene: 4-chlorobenzenesulfonyl chloride 5: 1) is loaded into the reactor. With constant stirring, the temperature of the reaction mixture was raised to 140 ^° C. and the mixture was kept at this temperature for 22 hours. The reaction mixture was treated as in Example 1. Yield 4-chloro-2 ', 4', 5'-trimethyl diphenyl sulfone 75%, melting point 132-135 ^o C.

Example 4. 8 g (30 wt.%) Of an Alumina catalyst containing 1.5 wt. % silica, 20 g (0.019 mol) of 1,4-dimethylbenzene, 6.7 g (0.004 mol) of benzenesulfonyl chloride (molar ratio of 1,4-dimethylbenzene: benzenesulfonyl chloride 5: 1), charged to the reactor and the temperature of the reaction mixture was increased with constant stirring up to 180 ^o C. The reaction mixture was kept at this temperature for 20 hours and treated analogously to example 1. The yield of 2,5-dimethyldiphenyl sulfone 70%, T _PL = 103 - 105 ^o C.

Example 5. 3.7 g (10 wt.%) Of an Alumina catalyst containing 2.0 wt. % silica, 20 g (0.18 mol) of chlorobenzene, 17.2 g (0.09 mol) of 4-methylbenzenesulfonyl chloride (ratio of chlorobenzene: 4-methylbenzenesulfonyl chloride 2: 1) is loaded into the reactor and the temperature in the reactor is raised to constant 140 ^o C. At this temperature, the reaction mixture was incubated for 18 hours and treated analogously to example 1. The yield of 4-chloro-4'-methyl diphenyl sulfone 85%, T _PL = 120-122 ^o C.

Claims (1)

A method for producing halogen and / or alkyl substituted diaryl sulfones by reacting the corresponding aromatic hydrocarbons with arenesulfonyl chlorides in the presence of an aluminum-containing catalyst at elevated temperature, characterized in that a heterogeneous alumina catalyst containing 1 to 2 wt.% Silicon oxide, taken in an amount of 10, is used - 30% of the reaction mass, and the process is carried out at 140 - 180 ^o C and a molar ratio of aromatic hydrocarbon: arenesulfonyl chloride 2 - 10: 1.