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Energy barriers to gas-phase unimolecular decomposition of mono- and dinitrotoluenes

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Abstract

Alternative paths of gas-phase unimolecular decomposition of three nitrotoluenes and six dinitrotoluenes, in particular homolytic dissociation of the C–N bond, nitro–nitrite rearrangement, intramolecular hydrogen transfer from the methyl to nitro group with formation of isomeric aci-nitrotoluenes, and various paths involving formation of bicyclic intermediates, have been studied at the DFT B3LYP/6-31+G(2df,p) level of theory using GAUSSIAN 09 software package. The most energetically favorable path for o-nitrotoluene and 2,3-, 2,4-, 2,5-, and 2,6-dinitrotoluenes is the formation of aci-nitrotoluenes. The effect of the substrate structure on the competition between different mechanisms of these reactions has been analyzed.

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Authors and Affiliations

  1. Kazan National Research Technological University, ul. K. Marksa 68, Kazan, Tatarstan, 420015, Russia

    G. M. Khrapkovskii, E. V. Nikolaeva, D. L. Egorov & A. G. Shamov

  2. Kazan Branch, Interinstitutional Supercomputer Center, Russian Academy of Sciences, ul. Lobachevskogo 2/31, Kazan, Tatarstan, 420111, Russia

    D. V. Chachkov

Authors
  1. G. M. Khrapkovskii
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  2. E. V. Nikolaeva
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  3. D. L. Egorov
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  4. D. V. Chachkov
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  5. A. G. Shamov
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Correspondence to G. M. Khrapkovskii.

Additional information

Original Russian Text © G.M. Khrapkovskii, E.V. Nikolaeva, D.L. Egorov, D.V. Chachkov, A.G. Shamov, 2016, published in Zhurnal Organicheskoi Khimii, 2016, Vol. 52, No. 6, pp. 806–820.

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Khrapkovskii, G.M., Nikolaeva, E.V., Egorov, D.L. et al. Energy barriers to gas-phase unimolecular decomposition of mono- and dinitrotoluenes. Russ J Org Chem 52, 791–805 (2016). https://doi.org/10.1134/S1070428016060063

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  • DOI: https://doi.org/10.1134/S1070428016060063

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