Thermal rearrangement of O-methyleneamino thiocarbamates

Abstract

The rate of the thermal, uncatalysed, [1,3] rearrangement of aromatic O-methyleneamino thiocarbamates to S-methyleneamino thiocarbamates in solution is insensitive to changes in both solvent polarity and substituent on ring and imino-carbon atoms, suggesting a transition state involving little charge separation. The occurrence of rearrangement via a radical pair is suggested by the detection by e.s.r. spectroscopy of aromatic iminyls, generated as transients during rearrangement.