Carbonate radicals react with aliphatic amines by a dual mechanism, viz. (i) hydrogen abstraction and (ii) electron transfer. The former is more probable with primary amines. Tertiary amines react via electron transfer. Both mechanisms may operate in secondary amines. Cyclic tertiary amines react with different rates and their relative reactivities are explained on the basis of the concept of Hoffmann's 'through bond' interaction. © 1985.