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A DFT study of inter- and intramolecular proton transfer in 2-selenobarbituric acid tautomers

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Abstract

DFT studies were employed to study proton transfer in selenobarbituric acid tautomers in different environments including gas-phase, polarized continuum model (PCM) of solvent and solvent-assisted models. The calculations were performed using WB97XD, CAM-B3LYP and B3LYP methods with the AUG-CC-PVTZ and 6-311++G** basis sets. Among various tautomeric conversions (between ten tautomers), three systems have been selected to study their thermodynamic and kinetic behaviors via proton transfer. The gas-phase calculations showed that only 2-selenoxodihydropyrimidine-4,6(1H,5H)-dione is the major tautomer and the rates of converting this tautomer to the other tautomers are small (<2.73 × 10−14). Using PCM solvation model, the amount of other tautomers versus the major tautomer is increased but the rate constants for proton transfer are slightly decreased. In the solvent-assisted proton transfer, the concentration of the second tautomer (6-hydroxy-2-selenoxo-2,3 dihydropyrimidin-4(1H)-one) was increased to 5 % (in methanol) in comparison with the major tautomer. More importantly, the rate constants for the most of intermolecular proton transfer in solvent-assisted models were intensively increased. Calculated values showed that these processes could be done in solvent-assisted models and other minor tautomers (with different chemical and biological behaviors) could be observed in these systems.

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Acknowledgments

We are grateful to National High-Performance Computing Center (NHPCC) at Isfahan University of Technology (http://nhpcc.iut.ac.ir) for providing computational facilities (Rakhsh supercomputer) for our work. This work has been supported by research affair of Isfahan University of technology.

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Authors and Affiliations

  1. Department of Chemistry, Isfahan University of Technology, 84156-83111, Isfahan, Iran

    Hossein Tavakol & Fariba Keshavarzipour

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  1. Hossein Tavakol
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  2. Fariba Keshavarzipour
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Correspondence to Hossein Tavakol.

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Tavakol, H., Keshavarzipour, F. A DFT study of inter- and intramolecular proton transfer in 2-selenobarbituric acid tautomers. Struct Chem 26, 1049–1057 (2015). https://doi.org/10.1007/s11224-015-0567-y

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  • DOI: https://doi.org/10.1007/s11224-015-0567-y

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