Effects of nitric acid concentration for nitration of fused [1,2,5]oxadiazolo[3,4-d]pyrimidine-5,7-diamine

Nitration reactions are very often used for the selective synthesis of novel, high performing nitramine-based materials. Now nitration reactions of the fused 5,7-diamino pyrimidine derivative 1, under different nitric acid concentrations were examined. Concentrated nitric acid gave selectively N-(5-amino-4,5-dihydro-[1,2,5]oxadiazolo[3,4-d]pyrimidin-7-yl)nitramide, 2, while the fused ring nitrate salt, 4, and ring open nitrate salt, 3 were obtained using low concentrations of nitric acid (<70%). In addition, the cesium salt of the fused nitramine derivative 5 was synthesized. All new compounds were isolated in high yields and comprehensively characterized by NMR, FTIR spectroscopy, and elemental analyses. The molecular structures of 2, 3, and 5 were analyzed by single X-ray crystallographic data. These compounds have high calculated heats of formation and high crystal densities. Detonation properties for compounds 2 and 3 were calculated using EXPLO5 software. Fused ring compound 2 (vD, 8549 m s-1; P, 29.62 GPa), and nitrate salt, 3 (vD, 8392 m s-1; P, 29.37 GPa) have superior detonation properties compared with TNT (vD, 7303 m s-1; P, 21.30 GPa). In addition, electrostatic potentials, two-dimensional (2D)-fingerprints, and Hirshfeld surface analysis were used to predict the sensitive properties of compounds 2 and 3. The experimental sensitives suggest possible applications with insensitive energetic applications.