Sodium hydroxide, reaction with aryl sulfonic acids

An aryl methane- or toluenesulfonate ester is stable to reduction with lithium aluminum hydride, to the acidic conditions used for nitration of an aromatic ring (HN03/H0Ac), and to the high temperatures (200-250°) of an Ullmann reaction. Aryl sulfonate esters, formed by reaction of a phenol with a sulfonyl chloride in pyridine or aqueous sodium hydroxide, are cleaved by warming in aqueous sodium hydroxide. ... 

Esters of aliphatic and aromatic sulfonic acids are conveniently prepared in high yields from alcohols and sulfonyl halides. A basic medium is required. By substituting sodium butoxide for sodium hydroxide in butanol, the yield of n-butyl p-toluenesulfonate is increased from 54% to 98%. Ethyl benzenesulfonate and nuclear-substituted derivatives carrying bromo, methoxyl, and nirro groups are prepared from the corresponding sulfonyl chlorides by treatment with sodium ethoxide in absolute ethanol the yields are 74-81%. Pyridine is by far the most popular basic medium for this reaction. Alcohols (C -Cjj) react at 0-10° in 80-90% yields, and various phenols can be converted to aryl sulfonates in this base. "... 

The chemistry of sulfones is dominated by the reactions of sulfonyl carbanions. The sulfone group has a unique ability to facilitate deprotonation of attached alkyl, alkenyl and aryl groups and will permit multiple deprotonation to yield polyanions. These properties, combined with the relative intertness of the sulfone (S02) group to nucleophilic attack, have made the S02 group the first choice for stabilisation of carbanions and account for the extensive application of sulfones in synthesis. Sulfonyl carbanions can be generated and reacted under a wide variety of conditions extending from aqueous phase transfer reactions using sodium hydroxide as base to the use of alkyllithiums in polar aprotic solvents. The reactivity of sulfonyl carbanions depends on the nature of the metal counterion (Li+, Na+, K+ and Mg2+ are the most important ones) and the presence of additives, e.g. TMEDA, HMPA and Lewis acids. 

Sodium mercaptides are prepared from the mercaptans and aqueous or alcoholic solutions of sodium hydroxide or alcoholic sodium eth-oxide. The sodium mercaptide reacts with halides, chlorohydrins, esters of sulfonic acid, or alkyl sulfonates [6] to give sulfides in yields of 70% or more. A recent report describes a general procedure for synthesizing aryl thioesters by a nucleophilic displacement of aryl halide with thiolate ion in amide solvents. No copper catalysis is necessary as in an Ullmann-type reaction. 

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