On the Viability of Nitronic Acids in the Decomposition of Nitroaromatics: A Theoretical Study of Nitronic Acids

The nitro - aci-nitro, keto - enol, and imine - enamine tautomeric processes in nitromethane, acetaldehyde, and acetaldimine were investigated at the G1 level of theory, in nitroacetaldehyde, 2- nitroacetaldimine, and 3-nitropropene at MP46-31G, in 2-nitroaniline, 2- nitrophenol, and 2-nitrotoluene at MP26-31 G, and in 2,6-dinitroaniline, 2,6- dinitrophenol, 2,6-dinitrotoluene, 2,4,6-trinitroaniline picramide, 2,4,6- trinitrophenolpicric acid, PA, and 2,4,6-trinitrotoluene NT at HF6-31 G. These studies demonstrate that the ease of tautomerization is in the order PA easiest, TNT then picramide, which parallels their sensitivity to impact. The nitronic acid tautomer of TNT is calculated at HF-6-31G to lie 39 kcalmol above TNT with a 65 kcalmol barrier with an extrapolated value of 48 kcalmol under MP2, while the nitronic acid tautomer of picaramide lies 48 kcalmol above picramide beyond a 51 kcalmol barrier. Cyclization and dehydration of the latter two nitronic acids should be overall exothermic processes. Nitronic acid, TNT, Picric acid, Picramide, Nitromethane, Cyclization, Nitroaromatics.