John L. Kice

CHAPTER 5 – DESULFONYLATION REACTIONS

A variety of reactions in organic sulfur chemistry involve elimination of sulfur dioxide. Some general considerations concerning the various types of mechanisms and intermediates likely to be involved in such “desulfonylation reactions” are first presented. This is followed by detailed consideration of the results of mechanistic studies of a number of specific desulfonylations. The particular reactions discussed are: The pyrolysis of sulfones, the peroxide-initiated decomposition of sulfonyl chlorides, and the thermal decompositions of chlorosulfites, sulfites and thiolsulfonates. In each case the probable mechanism for the reaction suggested by the experimental results is outlined and any exceptions to the usual behavior noted and discussed. Areas needing further investigation are indicated. n nFinally, attention is called to some important and interesting desulfonylation reactions which have not yet been subjected to mechanistic study.