Mercaptans sulfonyl chlorides

Arylsulfonyl chlorides are reduced by zinc dust and sulfuric acid at 0° to give high yields of thiophenols Tin and hydrochloric acid and a mixture of phosphorus, potassium iodide, and phosphoric acid have also been used. Preliminary experiments with lithium aluminum hydride on both alkyl- and aryl-sulfonyl chlorides gave 45 50% yields of mercaptans. Halogen atoms on the benzene ring are stable during the reduction. ... 

Oxidations by chlorine are limited to only few types of compounds. In organic solvents and pyridine [681] or hexamethylphosphoramide (HMPA) [682] as cosolvents, primary alcohols are oxidized to aldehydes and secondary alcohols to ketones [681, 682]. Secondary alcohols are oxidized in preference to primary alcohols [681]. Many oxidations with chlorine are carried out in aqueous media and involve sulfur-containing compounds. Mercaptans [683], alkyl thiolcarboxylates [683], thiocyanates [684], isothioureas [684], disulfides [655], and sulfinic acids [656] are transformed into sulfonyl chlorides. The chlorination of dimethyl disulfide in acetic anhydride yields methanesulfinyl chloride [657]. 

The oxidation of mercaptans with chlorine in water gives sulfonyl chlorides. Ethyl mercaptan and pentyl mercaptan afford ethanesulfonyl chloride and pentanesulfonyl chloride in yields of 73 and 78% at 5 and 1-5 C, respectively [6S3]. 

The reduction of sulfonyl chlorides may lead to sulfinates [265-267], thiosulfonates [267], disulfides, and mercaptans depending on the conditions in the presence of alkylating agents [266], sulfones or sulfides are among the products. 

The SO2 and SO groups of sulfur compounds produce sbong infrared bands in the 1400-1000 cm range. The expected S=0 stretching bands for sulfoxides, sulfones, sulfonic acids, sulfonamides, sulfonyl chlorides and sulfonates are given in Table 4.11. The other bonds involving sulfur, such as S-H, S-S and C-S, produce weaker infrared bands. Compounds, such as sulfides and mercaptans. 

The reaction of alkyl mercaptans and dialkyl disulfides with chlorine in an aqueous system yields alkane sulfonyl chlorides in good yield. 

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