Nitroacetonitrile is a useful synthetic precursor capable of participating in a wide range of reactions and enables the simple synthesis of annulated heterocyclic systems which are rapidly becoming promising new energetic materials.
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.
The reaction of diazotetrazole with nitroacetonitrile led to the isolation of the simple 1,2,4‐triazine‐based energetic 3‐azido‐5‐amino‐6‐nitro‐1,2,4‐triazine. It and related compounds were chemically characterized by NMR, IR, and single‐crystal X‐ray crystallography. Their energetic sensitivities (impact, friction) were experimentally determined and energetic performances calculated. The ability of 3‐azido‐5‐amino‐6‐nitro‐1,2,4‐triazine to form N‐oxides was also studied.
Bis(3‐nitro‐1H‐1,2,4‐triazol‐5‐yl)methane (BNTM) was synthesized in 79 % yield via the oxidation of 5,5'‐diamino‐3,3’‐methylene‐1H‐1,2,4‐triazole (DABTM) with titanium superoxide in a water and hydrogen peroxide solution. BNTM synthesized by this method was characterized via low‐resolution mass spectrometry (LRMS), nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), elemental analysis, and single crystal X‐ray crystallography for comparison with BNTM produced by traditional routes. The cesium, lithium, potassium, rubidium, sodium, and strontium salts of BNTM were characterized for their thermal stabilities and mechanical sensitives. Each of the salts possessed multiple hydrates, the loss of the associated water can clearly be seen by thermal gravimetric analysis (TGA). All the salts were less sensitive to impact than neutral BNTM and, except for the sodium and cesium salts, were less sensitive to friction. Single crystal X‐ray crystallography was utilized to analyze the crystal structures obtained for the cesium, strontium, and sodium salts.
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