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) associated with one of the two nitro groups. This tight association (-NO(2)(.-)M(+)) persists after solvent removal, and it renders the anion radical very susceptible to loss of metal nitrite. The slightest agitation of the solid potassium salt of DNT.- leads to detonation, and formation 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 comes from carbenes, and it is suggested that the HCN comes from an anthranil radical intermediate. The potassium anion radical salts of 1,3-dinitrobenzene, 2,6-dinitrotoluene, 1,3,5-trinitrobenzene, and 2,4,6-trinitrotoluene all readily lose KNO2, and the ease of C-NO(2)(.-)M(+) bond rupture increases with the degree of nitration. In the cases of the two trinitrated systems dissociation takes place immediately upon anion 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.