P-Chlorobenzenesulfonyl chloride

Zinc dust (120 g.) is added (30 minutes) with stirring to a mixture of 72 g. (0.34 mole) of p-chlorobenzenesulfonyl chloride (p. 72),... 

The reaction mixture was allowed to warm gradually to 50°C. The reaction was quenched by pouring into ice water. The aqueous suspension was heated to hydrolyze p-chlorobenzenesulfonyl chloride (II) to the water-soluble sulfonic acid. The desired product was filtered and washed with water until essentially neutral. Bis (4-chlorophenyl) sulfone was purified by recrystallization from benzene—m.p. 145°-147°C (4). Extremely low yields were obtained by this process. By contrast, yields in excess of 90% have been reported in processes that involve the reaction of chlorobenzene with sulfur trioxide and dimethyl or diethyl sulfate (5, 6). 

The sulfonate (1) is prepared by the reaction of 6-chloro-N-hydroxybenzo-triazole with p-chlorobenzenesulfonyl chloride under Schotten-Baumann conditions. ... 

Anisole (methyl phenyl ether) is extremely reactive towards sulfonation due to the presence of the strongly electron-donating (-fM) methoxy group. It therefore reacts with chlorosulfonic acid (two equivalents) at 0 °C to give mainly p-methoxybenzenesulfonyl chloride. With chlorobenzene, the chlorine atom exerts a strong electron-withdrawing (-1 effect) so sulfonation will be rather less easy than for benzene. Treatment of chlorobenzene with chlorosulfonic acid (four equivalents) at 25 C (3 hours) afforded p-chlorobenzenesulfonyl chloride (84%) and di(/7-chlorophenyl sulfone) (6%)." Chlorobenzene with chlorosulfonic acid (six equivalents) at 150-160 °C (8 hours) gave the 2,4-disulfonyl chloride. 

Chlorobenzene reacts with an equimolar amount of chlorosulfonic acid to give mainly the p-sulfonic acid together with a little of the sulfonyl chloride and the sulfone. With an excess of the reagent good yields of p-chlorobenzenesulfonyl chloride are obtained. The kinetics of the sulfonation of chlorobenzene with chlorosulfonic acid have been studied, and the reaction has been reported in several patents. These involved various modifications such as the use of excess reagent in hydrocarbon solvents containing alkali metal or ammonium salts, or a mixture of the reagent with thionyl chloride in the presence of sulfamic acid, sodium sulfate or dimethylformamide. In the reaction, the yield of 4,4 -dichlorodiphenyl sulfone can be increased under a variety of conditions the... 

Chlorobenzenesulfonyl chloride 216 Chlorobenzene (20 g) is added from a dropping funnel, during 2 h, to chlorosulfuric acid (60 g), which is cooled to —15°. The mixture is set aside with occasional shaking for 2 h at —5° to —10° and then for 12 h at room temperature, after which it is poured on ice. The oil is separated and distilled in a vacuum. The sulfonyl chloride (22 g m.p. 53°) passes over at 144°/15 mm recrystallization of the residue from glacial acetic acid gives pure bis-(/ -chlorophenyl) sulfone (5 g). 

Meerwein and his co-workers469 found that p-chlorobenzenesulfonyl chloride476 can be obtained from p-chlorobenzenediazonium chloride in liquid sulfur dioxide containing copper(i) chloride, and his school later elaborated... 

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