Impact of the acidic group on the hydrolysis of 2-dinitromethylene-5,5-dinitropyrimidine-4,6-dione

The hydrolysis mechanism and the kinetics of using 2-dinitromethylene-5,5-dinitropyrimidine-4,6-dione (NMP) to prepare the representative insensitive energetic material 1,1-diamino-2,2-dinitroethylene (FOX-7) in a nitric–sulfuric acid system are systematically investigated via a density functional theory (DFT) method. The impact of the co-existing acidic group of HSO(4)(−) as well as the solvent effects of the mixed acids on the hydrolysis of NMP are elucidated and discerned, and the proposed catalysis and promotion of the hydrolysis of NMP with HSO(4)(−) are verified. The HSO(4)(−)-catalyzed hydrolysis pathway is more favorable than the direct pathway as well as the H(2)O-catalyzed hydrolysis, indicating that HSO(4)(−) may be a promising catalyst for the preparation of FOX-7 in a mixed acid system. The present study is expected to provide a better understanding of the hydrolysis of NMP, and will significantly help with better preparation of FOX-7 and other nitro-energetic materials.