A mechanism for the electrochemical oxidation of diaryl disulfides in organic solvents is proposed. a difference is observed according to the nature of the solvent. In dichloromethane and in neutral conditions it is a two-electron process leading to the postulated cation Ar-S+. By reactions in situ with terminal alkynes in the presence of nucleophiles, alpha-oxothioesters of the type R-CO-CO-S-Ar were obtained.