Azuleno[6,5-d]thiazole (5a) and its 2-methyl derivative (8) were obtained by the deethoxycarbonylation of the corresponding diethyl azuleno[6,5-d]thiazole-5,7-dicarboxylate (4a) and 2-methyl derivative (6b) which were synthesized from diethyl 2-acetylamino-6-aminoazulene-1,3-dicarboxylate (1) in a few steps. Polybromination of 5a and 8 in 10% aqueous THF led to the corresponding 5-bromo-7,9-azulenequinono[6,5-d]thiazole (9a) and 2-methyl derivative (9b), respectively.