This article is the first in series of researches, dedicated to mechanisms of gas-phase monomolecular decomposition of nitrotoluenes. The article contains the results of quantum-chemical study of basic alternative mechanisms of primary act of thermal destruction of ortho-, meta- and para-nitrotoluenes, and also of 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dinitrotoluenes, and also of 2,4,6-trinitrotoluene, using the B3LYP/6-31+G(2df,p) density functional method. The enthalpies of activation and reaction were computed. It should be noted, that for compounds with hydrogen-containing substituent in ortho-position with respect to nitro-group, the minimal barrier is observed for the reaction of intramolecular transfer of hydrogen from methyl group to nitro-group, with formation of aci-nitrotoluenes. It is shown, that small monotone reduction for enthalpy of activation is observed for this process during the accumulation of nitro-groups. However, this trend is violated by the results obtained for 2,3-dinitrotoluene and for 2,5-dinitrotoluene. The correlation (with coefficient equal to 0,94) of changes for the enthalpy of activation and the enthalpy of reaction was found for the considered process.
квантово-химический расчет, нитротолуол, механизмы реакций, термическое разложение, quantum-chemical computation, nitrotoluene, mechanisms of reactions, thermal decomposition
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