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 1H NMR, 13C 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. The synthesis, X‐ray crystal structure, hydrolysis, nitrolysis of two potential precursors for the preparation of nitramine explosives (bicycle‐HMX and bi‐RDX) are reported. [ABSTRACT FROM AUTHOR]