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Structure and Conformational Analysis of 5,5-Bis(bromomethyl)-2,2-diphenyl-1,3-dioxane

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Abstract

The structure of 5,5-bis(bromomethyl)-2,2-diphenyl-1,3-dioxane was studied by 1H and 13C NMR spectroscopy and X-ray analysis. Its molecules in crystal adopt a chair conformation, whereas equilibrium between energy-degenerate chair invertomers exists in solution at room temperature. According to the low-temperature NMR data, the interconversion barrier amounts to 8.9 kcal/mol. The ring inversion path was simulated by DFT quantum chemical calculations using PBE/3ξ and (in some cases) RI-MP2/λ2 approximations, and the potential barrier to interconversion in different solvents was estimated by the cluster model. The calculated geometric parameters of the title compound were consistent with the experimental X-ray diffraction data, and the calculated interconversion barrier matched a cluster containing 5 molecules of methylene chloride in the nearest solvation shell of the substituted 1,3-dioxane molecule.

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Acknowledgments

Structural studies were carried out at the Agidel joint center (Institute of Petrochemistry and Catalysis, Russian Academy of Sciences).

Funding

This study was performed under financial support by the Ministry of Science and Higher Education of the Russian Federation (project no. 16.1969.2017/4.6).

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Authors and Affiliations

  1. Bashneft Public Corporation, Ufa, 450077, Russia

    Sh. Yu. Khazhiev

  2. Ufa State Petroleum Technological University, Ufa, 450062, Russia

    M. A. Khusainov & V. V. Kuznetsov

  3. Bashkir State Medical University, Ufa, 450008, Russia

    R. A. Khalikov & V. A. Kataev

  4. Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, 450075, Russia

    T. V. Tyumkina, E. S. Meshcheryakova & L. M. Khalilov

  5. Ufa State Aviation Technical University, Ufa, 450008, Russia

    V. V. Kuznetsov

Authors
  1. Sh. Yu. Khazhiev
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  2. M. A. Khusainov
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  3. R. A. Khalikov
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  4. V. A. Kataev
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  5. T. V. Tyumkina
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  6. E. S. Meshcheryakova
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  7. L. M. Khalilov
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  8. V. V. Kuznetsov
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Corresponding author

Correspondence to V. V. Kuznetsov.

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Russian Text © The Author(s), 2020, published in Zhurnal Organicheskoi Khimii, 2020, Vol. 56, No. 1, pp. 9–15.

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Khazhiev, S.Y., Khusainov, M.A., Khalikov, R.A. et al. Structure and Conformational Analysis of 5,5-Bis(bromomethyl)-2,2-diphenyl-1,3-dioxane. Russ J Org Chem 56, 1–6 (2020). https://doi.org/10.1134/S1070428020010017

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  • DOI: https://doi.org/10.1134/S1070428020010017

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