Nitroamino Triazoles: Nitrogen‐Rich Precursors of Stable Energetic Salts

Abstract

Abstract 1‐Nitroamino‐1,2,3‐triazole ( 5 ) was synthesized and its zwitterionic structure was established using single‐crystal X‐ray diffraction. The calculated detonation properties for 4‐nitroamino‐1,2,4‐triazole ( 2 ) ( P = 33.4 GPa, vD = 8793 m/s) and 1‐nitroamino‐1,2,3‐triazole ( 5 ) ( P = 33.0 GPa, vD = 8743 m/s) are comparable with RDX. A new family of energetic salts 7 – 21 based on either the 1‐nitroamino‐1,2,3‐triazolate or the 4‐nitroamino‐1,2,4‐triazolate anion were prepared and characterized by vibrational spectroscopy (IR), multinuclear NMR spectra, elemental analyses, density, TGA and DSC. The heats of formation (Δ f H° 298 ) and detonation properties for these stable salts were calculated using Gaussian 03 and Cheetah 4.0, respectively. Comparison of the properties of the 1,2,3‐ and 1,2,4‐triazolate salts indicates that while the 1,2,4‐derivatives are more stable thermally, the 1,2,3‐analogs invariably have higher heats of formation. In contrast to its salts, 1‐nitroamino‐1,2,3‐triazole ( 5 ) is extremely shock‐sensitive with an impact sensitivty of <1 J. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)