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Thermodynamic and kinetic studies of the retro-Diels-Alder reaction of 1,4-cyclohexadiene, 4H-pyran 4H-thiopyran, 1,4-dioxine, and 1,4-dithiine: a theoretical investigation

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Abstract

Theoretical studies of the retro-Diels-Alder reaction of 1,4-cyclohexadiene, 4H-pyran 4H-thiopyran, 1,4-dioxine, and 1,4-dithiine in the gas phase were carried out using DFT methods at the B3LYP/6–311 + G(d,p) levels of theory. The barrier height (ΔE‡) and thermodynamic parameters (ΔG‡ and ΔH‡) were estimated. The progress of the reactions was followed by means of the Wiberg bond indices. The synchronicity values of the reactions were calculated. The kinetic parameters were calculated for both reactions in 300–1200-K temperature range. Also, fitted equations to the gas phase Arrhenius equation were determined. Effect of the character and number of heteroatoms were illustrated on the thermodynamic and kinetic parameters.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Arak Branch, Islamic Azad University, Arak, Iran

    Elham Sheikh Ansari & Ali Forghaniha

  2. Department of Chemistry, Faculty of Science, East Tehran Branch, Islamic Azad University, Tehran, Iran

    Reza Ghiasi

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  1. Elham Sheikh Ansari
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  2. Reza Ghiasi
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  3. Ali Forghaniha
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Correspondence to Reza Ghiasi.

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Ansari, E.S., Ghiasi, R. & Forghaniha, A. Thermodynamic and kinetic studies of the retro-Diels-Alder reaction of 1,4-cyclohexadiene, 4H-pyran 4H-thiopyran, 1,4-dioxine, and 1,4-dithiine: a theoretical investigation. Struct Chem 30, 877–885 (2019). https://doi.org/10.1007/s11224-018-1241-y

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  • DOI: https://doi.org/10.1007/s11224-018-1241-y

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