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N ‐Oxide 1,2,4,5‐Tetrazine‐Based High‐Performance Energetic Materials
Author(s) -
Wei Hao,
Gao Haixiang,
Shreeve Jean'ne M.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405122
Subject(s) - tetrazine , detonation , oxide , materials science , density functional theory , oxygen balance , hydrogen peroxide , oxygen , chemistry , standard enthalpy of formation , thermal stability , explosive material , computational chemistry , organic chemistry
One route to high density and high performance energetic materials based on 1,2,4,5‐tetrazine is the introduction of 2,4‐di‐ N ‐oxide functionalities. Based on several examples and through theoretical analysis, the strategy of regioselective introduction of these moieties into 1,2,4,5‐tetrazines has been developed. Using this methodology, various new tetrazine structures containing the N ‐oxide functionality were synthesized and fully characterized using IR, NMR, and mass spectroscopy, elemental analysis, and single‐crystal X‐ray analysis. Hydrogen peroxide (50 %) was used very effectively in lieu of the usual 90 % peroxide in this system to generate N ‐oxide tetrazine compounds successfully. Comparison of the experimental densities of N ‐oxide 1,2,4,5‐tetrazine compounds with their 1,2,4,5‐tetrazine precursors shows that introducing the N ‐oxide functionality is a highly effective and feasible method to enhance the density of these materials. The heats of formation for all compounds were calculated with Gaussian 03 (revision D.01) and these values were combined with measured densities to calculate detonation pressures ( P ) and velocities ( ν D ) of these energetic materials (Explo 5.0 v. 6.01). The new oxygen‐containing tetrazines exhibit high density, good thermal stability, acceptable oxygen balance, positive heat of formation, and excellent detonation properties, which, in some cases, are superior to those of 1,3,5‐tritnitrotoluene (TNT), 1,3,5‐trinitrotriazacyclohexane (RDX), and octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX).