EXPLOSION AND ION ASSOCIATION CHEMISTRY OF THE ANION-RADICALS OF 2,4,6-TRINITROTOLUENE, 2,6-DINITROTOLUENE, AND TRINITROBENZENE

EPR analysis shows that the anion radical of 2,6-dinitrotoluene (DNT) in liquid ammonia exists with the counterion (either K+ or Nat) associ ated with one of the two nitro groups. This tight association (-NO(2)( .-)M(+)) persists after solvent removal, and it renders the anion radi cal very susceptible to loss of metal nitrite. The slightest agitation of the solid potassium salt of DNT.- leads to detonation, and formati on of KNO2 and polymer (in the solid phase) and CH4, HCN, H-2, and N2O (in the gas phase). Trapping experiments suggest that the methane com es from carbenes, and it is suggested that the HCN comes from an anthr anil radical intermediate. The potassium anion radical salts of 1,3-di nitrobenzene, 2,6-dinitrotoluene, 1,3,5-trinitrobenzene, and 2,4,6-tri nitrotoluene all readily lose KNO2, and the ease of C-NO(2)(.-)M(+) bo nd rupture increases with the degree of nitration. In the cases of the two trinitrated systems dissociation takes place immediately upon ani on radical formation in liquid ammonia. This observation is consistent with the fact that only the systems with two nitro groups vicinal to a methyl group yield HCN upon detonation.