Sulphenyl and Selenenyl Halides

Sulphenyl and Selenenyl Halides.—The preparation of these compounds by halogenolysis of disulphides and diselenides, a particular example being the preparation of the stable 3-nitropyridine-2-sulphenyl chloride and bromide, has not proved suitable for sulphenyl fluorides. Evidence for the existence of PhSF as an intermediate in the conversion of diphenyl disulphide into thianthrene has been provided by F n.m.r. studies. Addition of SClj to alkenes is rarely used, since 

References to addition reactions of sulphenyl halides with alkenes and alkynes are given in the Sulphides section. An incidental bonus from a study of the addition of PhSCl to adamantylideneadamantane is the formation of the 4e-chloro-derivative and PhSSPh, via an intermediate thiiranium salt. Sulphenyl and selenenyl chlorides have been used for the dehydration of aldoximes to nitriles. Whereas sulphinyl chlorides yield sulphinate esters with alkoxytri-methylsilanes, no reaction occurs with sulphenyl chlorides.  

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Preparation from Sulphenyl and Selenenyl Halides.—Most of the methods published in the period under review lead to -halogeno-sulphides through additions... 

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