N-denitration of octahydro-1, 3, 5, 7-tetranitro-1, 3, 5, 7-tetrazocine (HMX) by hydrazine catalyzed by palladium

In palladium-catalyzed reactions between HMX (1) and hydrazine, the nitramine was denitrated. The ultimate products depended on particular reaction conditions. The initial intermediate in the presence of excess hydrazine in organic solvents or water is the reactive species formaldazine (4). Under oxidizing conditions with catalyst, this reacts further to form 4-amino-4H-1, 2, 4-triazole (5) as a final product. In neat hydrazine as solvent, hexamethylenetetramine (2) and reactive intermediates such as 1, 2, 4-triazolidine (6) are formed in situ following N-denitration.