Aminoxyl (nitroxyl) radicals in the early decomposition of the nitramine RDX.
The explosive nitramine RDX (1,3,5-trinitrohexahydro-s-triazine) is thought to decompose largely by homolytic N-N bond cleavage, among other possible initiation reactions. Density-functional theory (DFT) calculations indicate that the resulting secondary aminyl (R2N·) radical can abstract an oxygen atom from NO2 or from a neighboring nitramine molecule, producing an aminoxyl (R2NO·) radical. Persistent aminoxyl radicals have been detected in electron-spin resonance (ESR) experiments and are consistent with autocatalytic "red oils" reported in the experimental literature. When the O-atom donor is a nitramine, a nitrosamine is formed along with the aminoxyl radical. Reactions of aminoxyl radicals can lead readily to the "oxy-s-triazine" product (as the s-triazine N-oxide) observed mass-spectrometrically by Behrens and co-workers. In addition to forming aminoxyl radicals, the initial aminyl radical can catalyze loss of HONO from RDX.
Chemical Informatics Research Group, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-8320, United States. karl.irikura@nist.gov
Karl K
KK
Irikura
D004578:Electron Spin Resonance Spectroscopy; D053834:Explosive Agents / Q000737:chemistry*; D007700:Kinetics; D009585:Nitrogen Dioxide / Q000737:chemistry; D009589:Nitrogen Oxides / Q000737:chemistry*; D009602:Nitrosamines / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry; D011789:Quantum Theory; D013816:Thermodynamics; D014227:Triazines / Q000737:chemistry*
D053834:Explosive Agents; D009589:Nitrogen Oxides; D009602:Nitrosamines; D014227:Triazines; C039900:nitroxyl; D009585:Nitrogen Dioxide; D010100:Oxygen; C009160:cyclonite