Acylsulfenyl chloride

Regarding the S-acyl alkoxy chalcogenides [RC(0)E0R E=S, Se, Te], a few sulfur derivatives 123 RC(0)S0R have been prepared from acylsulfenyl chlorides with alcohols in the presence of pyridine [100,102]. The aromatic derivatives 123 (R=aryl) can also be obtained in good yields using aroylsulfenyl bromides with alcohols [189,253]. 

The a-(alkylthio)ketones are dehydrogenated by phenylsulfenyl chloride (54). In this case chlorine transfer between the sulfur atoms of the reactants could be the initial and crucial step. There is little evidence asserting either a biphilic course or direct displacement at S during reaction of thiols with sulfenyl chlorides and acylsulfenyl chlorides (55). Both are soft interactions. 

Like the chlorides 153 and the bromides 154, treating phenylmercury thiocar-boxylates with iodine yields the acylsulfenyl iodides 155 in moderate yields (Scheme 20) [ 146]. Moreover, silver thiocarboxylates undergo S-iodination with JV-iodosuccinimide (NIS) to give 155 [148]. Trifluoroacetylsulfenyl iodide has been isolated [228]. The use of diphenylstannyl bis(thiocarboxylates) instead of PhHg(RCOS) is more effective [149]. 

---