Sulfenyl free radical

The free-radical chemistry of fluoroalkanesulfenyl chlorides with hydrocarbons was also investigated [S, 9], Depending upon the structures of the sulfenyl chloride and the hydrocarbon, these reactions yield as major products up to three of the following four types of organic compounds thiols, disulfides, sulfides, and chlorohydrocarbons (equation 6), Perfluoroisobutanesulfenyl chloride is unique m that the only major products detected are the thiol and chlorohydrocarbon [ ] (equation 6) (Table 3). 

Scheme 2 summarizes the mechanism for the formation of thiosulfonate from sulfinyl radicals it is shown that the sulfinyl radicals combine to give both yic-disulfoxides and O, S-sulfenyl sulfinates, although they may rearrange to thiosulfonates either via a free radical route or via a concerted mechanism. The reader is referred to the recent review of Freeman22, who has collected and discussed the vast amount of information published on yic-disulfoxides and O, S-sulfenyl sulfinates. 

Although very few studies of free-radical reactions of sulfenyl compounds have as yet been reported, irradiation with ultraviolet light enhances the rate of addition of CI3CSCI to olefins.218 Evidence for free-radical behavior is found in the easy decompositions which are observed for RSC1 under irradiation, e.g., the conversion of methanesulfenyl chloride to chloromethanesulfenyl chloride287 under the influence of sunlight. In the photoinitiated chlorination reaction with trichloro-... 

The reaction of the thiazoline sulfur with iodine depended upon the side chain and reaction conditions (Micetich and Morin, 1976). The thiazoline (162) reacted to give complex A or B depending upon the stoichiometry. Addition of water to complex A gave the symmetrical disulfide (246) which on further iodination yielded the 3-iodocepham (247). Complex B with water gave 247 directly. Other workers have reported catalytic effects of free radical initiators or heavy metal oxides in this transformation (W. Germ. Patent 2,534,811 Micetich and Morin, 1977). It was postulated that the sulfenyl iodide intermediate (248) was obtained on aqueous treatment of the original complexes which then spontaneously cyclized to the cepham derivative. 

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