Synthesis, Hydrolysis, Reduction and Nitrolysis of Glycoluril-Derived Precursors: Another Attempt toward the Synthesis of Nitramine Explosives

A new glycoluril derivative-1H, 4H, 5H, 8H-2, 3a, 4a, 6, 7a, 8a-hexaazacyclopenta[def]fluorene-4, 8-dione, hexahydro-2, 6-bis(phenylmethyl) (3) is strategically designed and synthesized through the reaction between glycoluril, formaldehyde and benzylamine with the optimized molar ratio of 1:6:2. Compound 3 is fully characterized by H-1 NMR, C-13 NMR, IR, MS and X-ray single crystal diffraction. Reduction of compound 3 delivers a potential precursor-imidazo[4, 5-d]imidazole, octahydro-hexahydro-2, 6-bis(phenylmethyl) (4) for the synthesis of novel nitramine explosives (i.e. bicyclo-HMX and bi-RDX). The nitration and hydrolysis of compound 4 are investigated in detail and three ring-opened molecules N, 2, 4-trinitro-benzenemethanamine (8a), N, 2-dinitro-benzenemethanamine (8b) and N-methylene-benzenemethanamine (9) are obtained.