Titanium Superoxide for the Oxidation of Amines: Synthesis of bis(3‐nitro‐1H‐1,2,4‐triazol‐5‐yl)methane and its Metal Salts

Abstract

AbstractBis(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.