A new preparative method of synthesis was developed for unsymmetrical and symmetrical disulfides. This method involves sulfenylation of sodium thiolates with N-arenesulfenyl-N,N'-bis(arenesulfonyl)sulfinamidines. Imination of unsymmetrical disulfides with sodium chloroamides of sulfonic acids occurs at the more nucleophilic sulfur atom, affording N,N'-bis(arenesulfonyl)sulfinamidines and symmetrical disulfides.