Oxidations of 3,6‐diamino‐1,2,4,5‐tetrazine and 3,6‐bis(s,s‐dimethylsulfilimino)‐1,2,4,5‐tetrazine

Abstract Oxidation of 3,6‐diamino‐1,2,4,5‐tetrazine (1) with most peracids gave 3,6‐diamino‐1,2,4,5‐tetrazine 1,4‐dioxide (3) as the major product; however, treatment of 1 with peroxytrifluoroacetic acid (PTFA) gave 3,6‐diamino‐1,2,4,5‐tetrazine 1‐oxide (4) as the major product along with a small amount of 3‐amino‐6‐nitro‐1,2,4,5‐tetrazine 2,4‐dioxide (5). Oxidation of 3,6‐bis(S,S‐dimethylsulfilimino)‐1,2,4,5‐tetrazine (6) with 3‐chloroperoxybenzoic acid (MCPBA) gave 3‐S,S‐(dimethylsulfilimino)‐6‐nitroso‐1,2,4,5‐tetrazine (7), which was oxidized further with dimethyldioxirane to 3‐(S,S‐dimethylsulfoximino)‐6‐nitro‐1,2,4,5‐tetrazine (8). All attempts to obtain 3,6‐dinitro‐1,2,4,5‐tetrazine (2) by further oxidation of 7 or 8 failed.