Methanesulfenyl chloride trichloro

As a continuation to the studies by Darwish and Braverman on the [2,3]-sigmatropic rearrangement of allylic sulfinates to sulfones, and in view of its remarkable facility and stereospecificity (see Chapter 13), Braverman and Stabinsky investigated the predictable analogous rearrangement of allylic sulfenates to sulfoxides, namely the reverse rearrangement of that attempted by Cope and coworkers . These authors initiated their studies by the preparation of the claimed allyl trichloromethanesulfenate using the method of Sosnovsky . This method involves the reaction between trichloro-methanesulfenyl chloride and allyl alcohol in ether at 0 °C, in the presence of pyridine (equation 6). 

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-... 

Preparation. The reagent is prepared in 78% yield by oxidation of trichloro-methanesulfenyl chloride (Stauffer Chem. Co.) with hydrogen peroxide in acetic acid. ... 

Sodium fluoride [1, 1073-1074, before reference]. Sodium fluoride suspended in nonaqueous tetramethylene sulfone, acetonitrile, or DMF has been found to exchange halogen readily with carboxylic acid chlorides, a-chloro ethers, trichloro-methanesulfenyl chloride, POCl3, etc.2 ZG. W. Tullock and D. D. Coffman, J. Org.. 25, 2016 (1960)... 

A soln. of ethyl N-methyl-thionocarbamate in benzene added to a soln. of trichloro-methanesulfenyl chloride in the same solvent, stoppered immediately, and allowed to stand for 1 hr. crude tri-chloromethyl N-methylcarba-moyl disulfide. 

---