Density functional and ab initio study of the tautomeric forms of 3-acetyl tetronic and 3-acetyl tetramic acids

Skylaris, C.-K., Igglessi-Markopoulou, O., Detsi, A. and Markopoulos, J. (2003) Density functional and ab initio study of the tautomeric forms of 3-acetyl tetronic and 3-acetyl tetramic acids. Chemical Physics, 293 (3), 355-363. (doi:10.1016/S0301-0104(03)00359-8).

Record type: Article

Abstract

We propose all the accessible paths of interconversion between the tautomers of 3-acetyl tetronic and 3-acetyl tetramic acids by performing calculations with the density functional B3LYP method and the ab initio MP2 method. Our findings clarify at the atomic level the mechanisms of the equilibria between these tautomers, a topic so far only partially understood on the basis of studies by nuclear magnetic resonance (NMR) spectroscopy. We show that thermal effects via relative Gibbs free energies ?G must be taken into account in order to reach good quantitative agreement with the available experimental information on the ratios of the most stable tautomers. The calculated 1H and 13C chemical shifts are in agreement with the experimental values from NMR spectroscopy.

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