This article presents the results of quantum-chemical study of mechanism of isomerization reaction of o-nitrotoluene, 2,3-, 2,4-, 2,5-, 2,6-dinitrotoluenes and 2,4,6-trinitrotoluene to nitrites (or nitro-nitrite rearrangement reaction, NNR).The study was performed using B3LYP method, with 6-31+G(df,p) set of basic functions. It is ascertained, that enthalpy of activation for NNR process of nitrotoluenes is at 20-40 kJ/mole less than D(C-N). This fact increases its influence on the total rate constant during the decrease of temperature, in comparison with the radical mechanism. It is shown, than during the number increase of nitro-groups in molecules of nitrotoluenes the difference between the values of D(C-N) and enthalpy of NNR activation is reduced. In addition, the noticeable decrease of its difference as the result of presence of nitro-groups in meta- and para-positions is observed. This fact allows the supposition: it is possible to ascertain during the experiment, that for meta- and para-substituted nitrotoluenes the influence of NNR processes on effective constant of thermal decomposition reaction of nitrotoluenes in gas phase exists.
квантово-химический расчет, нитротолуол, механизмы реакций, термическое разложение, quantum-chemical calculation, nitrotoluene, mechanisms of reactions, thermal decomposition
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