It has been found that tetracyclic hexahydro-1, 3, 5-triazines react with arenethiols to give 2-arylthio-substituted alicyclic amines. This new reaction provides a useful method for the introduction of arylthio groups at the α-position of alicyclic amines. The reaction with thioglycolate gives bicyclic thiazolidine derivatives, some reactions of which are also described.