Generation of nitrenes from alkanamidates and alkanesulphonamidates

Abstract

N-Trimethylammoniododecanesulphonamidate and N-trimethylammoniododecanamidate have been degraded thermolytically and photolytically in nonaqueous solvents. Thermal decomposition of the sulphonamidate yielded a sulphonyl nitrene which was trapped by nucleophiles. The sulphonamidate was stable towards u.v. radiation. The alkanamidates decomposed thermally to give undecyl isocyanate by a concerted intramolecular process which did not involve the formation of a nitrene intermediate. Dodecanoyl nitrene, generated by photolysis of the alkanamidated in dimethyl sulphoxide, has been compared with similar nitrenes obtained photolytically from acyl azides. The electronic states of the nitrene intermediates are discussed.