Molecular modeling of the mechanisms of thermolysis of nitramino-1,2,4-triazoles

Modeling of the probable mechanisms of the thermolysis of C-and N-nitramino-1,2,4-triazoles has been carried out by methods of mathematical chemistry. It was established that the formation is possible of a more diverse spectrum of products in their destruction than was previously recorded by different experimental methods. Subsequent assessment of the thermochemical preference for pathways of decomposition of the compounds was carried out by the density functional method in the B3LYP/6-31G* approach. It was determined that the thermal destruction of C-and N-nitramino-substituted polynitrogen heterocycles, capable of tautomeric conversion, was most probably through the thermochemically least stable nitramine form. Thermal decomposition of the considered tautomers is preferred at the NNO₂ fragment and not at the triazole ring. The direction of the structural stabilization of the investigated compounds has been clarified by comparison of the geometric, electronic, and thermochemical characteristics of C-NNO₂-and N-NNO₂-substituted 1,2,4-triazoles. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1467–1495, October, 2006.