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A series of derivatives of 6-amino-tetrazolo[1,5-b][1,2,4,5]tetrazine have been synthesized for the first time. All the studied compounds have been shown to exist in the tetrazole form at ambient and elevated temperatures. The most interesting of 6-amino-tetrazolo[1,5-b][1,2,4,5]tetrazine derivatives were studied with respect to their combustion and thermal decomposition behaviors. 6-Amino-tetrazolo[1,5-b][1,2,4,5]tetrazine was found to possess explosive characteristics similar to those of primary explosives.