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Computational investigation of thermal decomposition mechanism of 5-nitro-5-R-1,3-dioxane compounds

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Abstract

This paper features the results of the computational study of thermal decomposition reaction of 5-nitro-5-R-1,3-dioxane compounds, with R = H, Br, and CH3. Computational calculations were performed with M06-2X, MPWB1K, PBE0 and ωB97X-D functionals, and 6–311 + G(d,p) basis set in gas phase and also in solution with DMSO, at different temperatures. The kinetic and thermodynamic data obtained indicate a favoring of the reaction when the molecule presents substituent groups in position 5 and when carried out in DMSO, the stability of the molecules in their energetic components was discussed, too. For R = H two different reaction mechanisms were proposed and studied. Wiberg bond indices were obtained for the reactions studied and the results were examined in terms of bond formation and bond breaking progress as well.

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Data availability

The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Not applicable.

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Acknowledgements

The authors are grateful for the support received from the Universidad Nacional de Colombia – Medellin Headquarters during the research and publication stages of this work. S. Q. also thanks Dirección General de Investigaciones of Universidad Santiago de Cali (DGI), Santiago de Cali. P. R. also thanks Instituto Tecnológico Metropolitano (ITM).

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Authors and Affiliations

  1. Laboratorio de Fisicoquímica Orgánica, Facultad de Ciencias, Universidad Nacional de Colombia, Medellin, 050034, Colombia

    Pablo Ruiz & Jairo Quijano

  2. Facultad de Ciencias Exactas Y Aplicadas, Instituto Tecnológico Metropolitano, Medellin, Colombia

    Pablo Ruiz

  3. Programa de Microbiología, Facultad de Ciencias Básicas, Universidad Santiago de Cali, Cali, Colombia

    Silvia Quijano

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  1. Pablo Ruiz
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Contributions

The contribution of each author listed is based on Silvia Quijano and Pablo Ruiz, who made a substantial contribution to the conception and design, data acquisition and analysis, and interpretation of the data; Pablo Ruiz and Jairo Quijano drafted the article and critically reviewed the intellectual content. All the authors read and approved the final manuscript.

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Correspondence to Pablo Ruiz.

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Ruiz, P., Quijano, S. & Quijano, J. Computational investigation of thermal decomposition mechanism of 5-nitro-5-R-1,3-dioxane compounds. Struct Chem 33, 1149–1155 (2022). https://doi.org/10.1007/s11224-022-01891-6

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  • DOI: https://doi.org/10.1007/s11224-022-01891-6

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