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Theoretical study of substituent and solvent effects on the thermodynamics for cis/trans isomerization and intramolecular rearrangements of 2,2′-diphenoquinones

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Abstract

Enthalpies (Δisom H o(g) ), Gibbs free energies (Δisom G o(g) ), and equilibrium constants (log K isom) for the trans → cis isomerization of various 3,3′-, 4,4′-, and 5,5′- disubstituted 2,2′-diphenoquinones with a range of electron withdrawing and releasing moieties (methyl, fluoro, chloro, bromo, trifluoromethyl, and amino) were calculated in the gas phase and in the solvent phase (n-hexane, benzene, n-octanol, acetonitrile, and water). In the gas phase, the trans isomer of the parent and all substituted 2,2′-diphenoquinones is predicted to be more thermodynamically stable than the cis configuration, with log K isom ranging from −2.8 to −7.0. For all compounds, increasing solvent polarity/proticity progressively favors shifting the cis/trans equilibrium towards greater contributions of the cis configuration and substantially increases the log K isom by up to 5.1 units relative to the gas phase. In polar protic and polar aprotic solvents, the estimated log K isom ranges as low as −0.4, indicating significant populations of the cis isomers should be present. The findings support the polar solvent phase mechanistic predictions for a cis configuration of 2,2′-diphenoquinones participating in the thermal transformation of trans-2,2′-diphenoquinones to oxepino[2,3-b]benzofurans. With limited exceptions for some amino derivatives, the cis-2,2′-diphenoquinone to oxepino[2,3-b]benzofuran isomerization is expected to be thermodynamically favorable for all substituents/phases under consideration. The cis-2,2′-diphenoquinone to oxepino[2,3-b]benzofuran rearrangement is predicted to become less thermodynamically favored with increasing solvent polarity/proticity.

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Acknowledgments

This study was made possible by the facilities of the Western Canada Research Grid (WestGrid: project 100185), the Shared Hierarchical Academic Research Computing Network (SHARCNET: project sn4612), and Compute/Calcul Canada. We extend sincere thanks to an anonymous reviewer whose suggestions to include calculations on the oxepino[2,3-b]benzofuran systems and the various isodesmic reactions greatly improved the quality of our study.

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  1. Ecologica Research, 301-1965 Pandosy Street, Kelowna, BC, V1Y 1R9, Canada

    Sierra Rayne

  2. Department of Chemistry, Okanagan College, 583 Duncan Avenue West, Penticton, BC, V2A 8E1, Canada

    Kaya Forest

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  1. Sierra Rayne
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Correspondence to Sierra Rayne.

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Rayne, S., Forest, K. Theoretical study of substituent and solvent effects on the thermodynamics for cis/trans isomerization and intramolecular rearrangements of 2,2′-diphenoquinones. Struct Chem 22, 615–625 (2011). https://doi.org/10.1007/s11224-011-9735-x

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