Computational study of TNT synthesis in solvated nitration reaction systems

Mononitrotoluene (MNT) was incorporated into solvated reaction systems and was subjected to subsequent nitration (electrophilic and free radical substitution) to obtain corresponding dinitrotoluene (DNT) and trinitrotoluene (TNT) products. In the electrophilic nitration system, the energy barrier of the reaction to produce o,p‐dinitrotoluene from p‐nitrotoluene was found to decrease from 62.7 to 14.7 kJ/mol to 9.2 kJ/mol in solventless, hydrated, and methanol‐solvated molecular reaction systems, respectively. Further nitration to produce TNT in related solventless and solvated systems also led to a stepwise decreasing trend in the required energy, from 297.6 to 118.6 kJ/mol to 42.8 kJ/mol. Comparative synthesis using ·NO₂ as the nitrating reagent to obtain o,p‐DNT or TNT in the hydrated system shows a lower reaction energy barrier than that of the same reaction in the solventless system. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009