Increasing the limits of energy and safety in tetrazoles: dioximes as unusual precursors to very thermostable and insensitive energetic materials

• Published in: Journal of materials chemistry. A, Materials for energy and sustainability Materials for energy and sustainability, 2023-06, Vol.11 (24), p.12896-1291
• Main Authors: Singh, Jatinder, Staples, Richard J, Shreeve, Jean'ne M
• Format: Article
• Language: English
• Subjects: Construction sites; Detonation; Diketones; Energetic materials; Ethane; Heat of formation; Precursors; Safety; Tetrazoles; Thermal stability
• ISSN: 2050-7488; 2050-7496
• DOI: 10.1039/d2ta09324c

Donor-acceptor hydrogen (H)-bonding contributes to good temperature resistance for energetic compounds. Now we report a strategy which maximizes donor-acceptor H-bonding sites in the construction of new energetic compounds. The straightforward synthesis of 1,2-di(1 H -tetrazol-5-yl) ethane-1,2-dione dioxime ( 2 ), as an unusual energetic precursor to highly thermostable and insensitive energetic materials was achieved in four steps from glyoxal (40% in water). The oxime group in compound 2 acts as a H-bond donor and acceptor and its salt formation reaction with hydroxylamine maximizes H-bonding interactions. Dihydroxylammonium 1,2-di(1 H -tetrazol-5-yl) ethane-1,2-dione, 3 , exhibits high thermal stability (285 °C) and insensitivity to impact (>60 J) and friction (>360 N) owing to the presence of donor-acceptor H-bonds and wave-like crystal packing. It has high heat of formation (524.3 kJ mol −1 ) and high detonation velocity of 9114 ms −1 . Compound 3 exhibits high safety, ultrahigh power and good compatibility, which make it a potential high-energy-density material for practical use. Unusual thermostable and insensitive high-energy compounds which contain dioximes with donor-acceptor H-bond sites, were synthesized from glyoxal (40% in water) in straightforward steps.