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

Abstract

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.