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Theoretical study on the isomerization and tautomerism in barbituric acid

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Abstract

Isomerization and tautomerism of 16 isomers of barbituric acid (BA) were studied at the MP2 and B3LYP levels of theory. Activation energies (E a), imaginary frequencies (υ), and Gibbs free energies (ΔG #) of the amine-imine and keto-enol tautomerisms and O–H internal rotations were calculated. The activation energies of amine-imine tautomerisms were in the range of 110–200 kJ/mol and for keto-enol tautomerisms were larger than 200 kJ/mol. The calculated activation energies of internal O–H rotations were smaller than 60 kJ/mol. Effect of micro-hydration on the transition state structures and activation energies of the tautomerisms were also investigated. Water molecule catalyzed the tautomerisms and decreased the activation energies of both the amine-imine and keto-enol tautomerisms about 100–120 kJ/mol.

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Acknowledgments

The authors wish to acknowledge Isfahan University of Technology for financial support.

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Authors and Affiliations

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

    Younes Valadbeigi, Hossein Farrokhpour & Mahmoud Tabrizchi

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  1. Younes Valadbeigi
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  2. Hossein Farrokhpour
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  3. Mahmoud Tabrizchi
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Correspondence to Hossein Farrokhpour.

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Valadbeigi, Y., Farrokhpour, H. & Tabrizchi, M. Theoretical study on the isomerization and tautomerism in barbituric acid. Struct Chem 25, 1805–1810 (2014). https://doi.org/10.1007/s11224-014-0452-0

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  • DOI: https://doi.org/10.1007/s11224-014-0452-0

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