Can N-oxidation alleviate the energy-safety contradiction of energetic materials?

Selective Synthesis and Characterization of the Highly Energetic Materials 1‐Hydroxy‐5H‐tetrazole (CHN4O), its Anion 1‐Oxido‐5H‐tetrazolate (CN4O−) and Bis(1‐hydroxytetrazol‐5‐yl)triazene

“…Due to the intermediate formation of 5-diazonium-1-hydroxytetrazole, Scheme 1. Synthesis of 1-hydroxy-5H-tetrazole (1) and its salts thereof (2-7), as well as the synthesis of bis(1-hydroxytetrazol-5-yl)-triazene (8) and its salts thereof (9)(10)(11)(12)(13)(14)(15). Hx + : hydroxylammonium; Hz + : hydrazinium; G + : guanidinium.…”

“…All crystal densities are recalculated to their respective room temperature crystal density. Crystal datasets were deposited in the CSD database and can be obtained free of charge with the following codes: CCDC 2088975 (1), 2088974 (2 a), 2088980 (2 b), 2088977 (3), 2088979 (4), 2088985 (5), 2088982 (6), 2088986 (7), 2088988 (8), 2088983 (9), 2088978 (10), 2088976 (11), 2088987 (12), 2088981 (13) and 2088984 (15). 1-Hydroxy-5H-tetrazole (1) crystallizes in the monoclinic space group P2 1 /n.…”

“… [5] General protocols to further increase the enthalpy of formation of tetrazoles include N ‐oxidation by Oxone®, [6] HOF, [7] or H 2 O 2 , [8] which also has the advantage of increasing the oxygen balance and crystal density. [9] In 2012, Klapötke et al . [10] obtained dihydroxylammonium‐5,5’‐bistetrazolyl‐1,1’‐diolat (TKX‐50) through the N ‐oxidation of 5,5’‐bistetrazole followed by formation of the hydroxylammonium salt.…”

“…[5] General protocols to further increase the enthalpy of formation of tetrazoles include N-oxidation by Oxone®, [6] HOF, [7] or H 2 O 2 , [8] which also has the advantage of increasing the oxygen balance and crystal density. [9] In 2012, Klapötke et al [10] obtained dihydroxylammonium-5,5'-bistetrazolyl-1,1'-diolat (TKX-50) through the N-oxidation of 5,5'-bistetrazole followed by formation of the hydroxylammonium salt. This compound possesses excellent detonation properties while being thermally stable (221 °C) and moderately sensitive towards impact (20 J) and friction (120 N), thus being stable enough to be safely used as a high-performing secondary explosive.…”

Accelerating Molecular Design of Cage Energetic Materials with Zero Oxygen Balance through Large-Scale Database Search

“…The molecules of cage structure have been generally applied in plenty of fields, such as the therapeutic, sensing, and catalysis fields. − In particular, in the field of energetic materials (EMs), the internal strain energies increase the energy density, as shown in Figure a, and cage EMs have attracted much attention. − The cage EMs are commonly designed based on the direct nitrification of experimentally available cage scaffolds. For example, ONC (octanitrocubane) with zero oxygen balance was proposed on the basis of cubane at a Working Group Meeting on High-Energy Compounds in 1981 and then was successfully synthesized after 18 years (See Figure b.)…”