THIOLSULFONATES AND SULFINATES

Thiolsulfonates decompose thermally according to first-order kinetics with the production of sulfides, sulfur dioxide, hydrocarbons and other products resulting from secondary decompositon of a thioaldehyde 

Sulfinic acids are thought to be produced by a side reaction during the homogeneous first-order decomposition of thiosulfonates, and were then postulated to decompose to sulfur dioxide and hydrocarbons by a free radical mechanism . 

In a separate study of the decomposition of sulfinic acids in the absence of solvent at 200 °C the major products were sulfur dioxide and alkenes . Minor products were water, carbon dioxide, carbon monoxide, carbonyl sulfide and sulfur. The reaction is considered to proceed by a unimolecular free radical mechanism, although kinetic evidence is lacking. Olefin formation results from transfer reactions followed by elimination and one plausible pathway is 

The postulated mechanism resembles that proposed for the thermal decomposition of alkanesulfonyl chlorides. 

Another class of sulfoxidic substances, the aryl thiosulfinates ArS(0)SAr, which have recently been prepared in an optically active form, exhibit exceptionally high optical lability Racemization of thiolsulfinates may occur in an uncatalysed path involving pyramidal inversion at the sulfoxide sulfur. Reaction rate coeffi- 

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