Various thioamides were found to react readily with peroxyphosphorus intermediate which is generated from phenylphosphonic dichloride and potassium superoxide in anhydrous acetonitrile at -8~-4℃ to convert into the corresponding amides in excellent yields. Desulfurization of thioamide by this method appears to be initiated by formation of unstable sulfine resulting from the reaction of thioamide with peroxyphosphorus intermediate.
Reaction of sulfoxides with peroxyphosphorus intermediate afforded corresponding sulfone and α-chlorosulfoxides. The ratio of the two products was varied by the electronic effect of the substiuents, temperature and the mole ratio of phenylphosphonic dichloride and potassium superoxide.