NUCLEOPHILIC-SUBSTITUTION REACTION OF 4-BROMO-BENZO[1,2-C-3,4-C']BIS[1,2,5]THIADIAZOLE AND REDUCTION OF HYDROXY AND METHOXY DERIVATIVE TO THE CORRESPONDING 1,2,3,4-BENZENETETRAAMINE

Bromobenzo[1,2-c;3,4-c]bis[1,2,5]thiadiazole (2a) reacted with a series of nucleophiles to give alkoxy-, propylthio-, and amino-substituted derivatives (3,8, and 9). Reaction of 2a with allyl alcohol at room temperature gave allyl ether (3e) which, on being heated, rearranged to 4-allyl-5-hydroxy derivative (4). Treatment of methoxy and ethoxy derivatives (3a and 3b) with hydrobromic acid gave hydroxy compound (5). Reduction of 3a and 5 gave the corresponding 1,2,3,4-benzenetetraamine (10.3HCl) and (11.2HCl), respectively. Reduction of piperidino derivative (9b) gave a mixture of hydrochlorides of 1,2,3,4-benzenetetraamine (1a), 11, and 5-piperidino-1,2,3,4-benzenetetraamine (12).