An unusual ring-expansion reaction of 4-amino-1,1-dioxo-[1,2,3,5]-thiatriazoles has been identified that produces the relatively rare 5-amino-1,1-dioxo-[1,2,4,6]-thiatriazines and. Initial alkylation of the thiatriazole with alpha-halo-esters at N-3 produces alpha-substituted esters which, under basic reaction conditions, undergo opening of the thiatriazole ring and re-closure to a thiatriazine ring. Similar alkylations of with diethyl chloromalonate and ethyl dichloroacetate lead to the loss of SO2 and the production of triazine and triazole, apparently by an initial alkylation at N-5. The reaction of with phenacyl bromides or a phenacyl dibromide forms fully unsaturated 5-amino-1,1-dioxo-[1,2,4,6]-thiatriazines.