Ammonia with sulfonyl halides

Sulfonyl chlorides as well as esters and amides of sulfonic acids can be hydrolyzed to the corresponding acids. Sulfonyl chlorides can by hydrolyzed with water or with an alcohol in the absence of acid or base. Basic catalysis is also used, though of course the salt is the product obtained. Esters are readily hydrolyzed, many with water or dilute alkali. This is the same reaction as 10-4, and usually involves R —O cleavage, except when R is aryl. However, in some cases retention of configuration has been shown at alkyl R, indicating S—O cleavage in these cases. Sulfonamides are generally not hydrolyzed by alkaline treatment, not even with hot concentrated alkali. Acids, however, do hydrolyze sulfonamides, but less readily than they do sulfonyl halides or sulfonic esters. Of course, ammonia or the amine appears as the salt. However, sulfonamides can be hydrolyzed with base if the solvent is HMPA. ... 

The most interesting behavior of the three dianhydrides is found in the displacement reactions of their 0-sulfonyl derivatives, and at present it seems that the reported results may be covered by three general rules. (1) Displacement of sulfonyloxy groups from the 0-sulfonates may be achieved under certain conditions, and occurs with inversion of configuration at the point of displacement. (2) Ammonia and halide ions displace sulfonyloxy groups, but alkali hydroxides (and perhaps alkoxides) merely hydrolyze the sulfonate esters by 0-sulfonyl fission, with retention of configuration. (3) Displacements by halide ions are possible only for endo sulfonyloxy groups. These rules are only tentative, and may be modified when more sulfonyloxy compounds, and their behavior to a wider variety of anions, have been studied. 

The sulfonyl chloride is prepared from the aromatic halide and chlorosulfonic acid in chloroform or without solvent. The sulfonamide is obtained from the sulfonyl chloride with concentrated ammonia or dry ammonium carbonate. 

Chlorosulfonic acid is widely used in organic qualitative analysis to prepare solid derivatives from liquid or low melting aromatic compounds, e.g. hydrocarbons, halides and ethers." The procedure involves conversion of the aromatic compound into the sulfonyl chloride, which is subsequently reacted with ammonia to yield the solid sulfonamide derivative which is suitable for melting point determination, Chlorosulfonic acid reacts with carboxylic acid anhydrides to give excellent yields of the acid chlorides (Equation 11). 

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