Energetic 1,2,4-Triazines: 3,5-Diamino-6-nitro-1,2,4-triazine and Its Oxide

Abstract

3,5-Diamino-6-nitro-1,2,4-triazine (DANT) was identified as a potentially insensitive energetic material with high symmetry and planar geometry yielding improved π–π stacking. The straightforward generation of this energetic 1,2,4-triazine was accomplished by azide to amine reduction of 5-amino-3-azido-6-nitro-1,2,4-triazine (AANT) with triphenylphosphine via a modified Staudinger reaction. Oxidation of DANT using potassium peroxymonosulfate triple salt produces the triazine N-oxide 3,5-diamino-6-nitro-1,2,4-triazine-2-oxide (DANTX). DANT and DANTX were characterized using mass spectroscopy, multinuclear NMR spectroscopy, infrared spectroscopy, and elemental analysis. The molecular structure and density of DANT (1.778 g cm–3) were determined by single-crystal X-ray diffraction indicating a graphite-like packed structure. Crystallization of DANTX yielded low-density (1.747 g cm–3) and high-density (1.852 g cm–3) polymorphs. Both DANT and DANTX were characterized as energetic materials in terms of sensitivity toward impact, friction, and thermal stimuli, and calculated detonation parameters are reported.