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

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.

Cupric coordination compounds with multiple anions: a promising strategy for the regulation of energetic materials

“…[34][35][36][37] At present, there are many studies on methylene bridged bis(triazole), but mainly on C-methylene-C bridged compounds, such as 3,3 ′ -bis (5-amino-1,2,4-triazolyl)methane, 3,3 ′ -bis(5-nitroamino-1,2,4-triazolyl) methane, 3,3 ′ -bis(4,5-diamino-1,2,4-triazol)methane, and 3,3 ′bis(5-nitro-1,2,4-triazolyl)methane, while there are few studies on N-methylene-C bridged bis(triazole). 29,[38][39][40] Owing to the bond energy of N-C bonds being higher than that of C-C bonds, N-methylene-C-bridged compounds exhibit higher energy than C-methylene-C-bridged compounds because of N-C bonds at multiple bridging positions. 41 Ammonium perchlorate (AP) is a widely used solid oxidant, especially in solid propellants.…”

Novel family of nitrogen-rich energetic (1,2,4-triazolyl) furoxan salts with balanced performance

“…However, it is known that NH-fragment of the 1,2,4-triazole ring is weakly acidic ( Garratt, 1996 ) and may stimulate corrosivity which is undesired for any potential application. Although examples on the preparation of energetic salts bearing a 1,2,4-triazolate anion are rather scarce (except NTO-based those) ( Parisi et al, 2021 ; Creegan et al, 2022 ), such strategy may serve as a convenient solution to overcome this issue. High-energy salts usually have acceptable thermal stability (>150°C) and moderate sensitivity to mechanical stimuli, while owing to the high nitrogen content these metal-free salts have a high level of environmental compatibility ( Larin et al, 2019 ; Larin and Fershtat, 2021 ).…”