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Detection of tautomer proportions of dimedone in solution: a new approach based on theoretical and FT-IR viewpoint

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Abstract

Molecular structures of stable tautomers of dimedone [5,5-dimethyl-cyclohexane-1,3-dione (1) and 3-hydroxy-5,5-dimethylcyclohex-2-enone (2)] were optimized and vibrational frequencies were calculated in five different organic solvents (dimethylsulfoxide, methanol, acetonitrile, dichloromethane and chloroform). Geometry optimizations and harmonic vibrational frequency calculations were performed at DFT 6-31+G(d,p), DFT 6-311++G(2d,2p), MP2 6-311++G (2d,2p) and MP2 aug-cc-pVDZ levels for both stable forms of dimedone. Experimental FT-IR spectra of dimedone have also been recorded in the same solvents. A new approach was developed in order to determine tautomers’ ratio using both experimental and theoretical data in Lambert–Beer equation. Obtained results were compared with experimental results published in literature. It has been concluded that while DFT 6-31+G(d,p) method provides accurate enol ratio in DMSO, MeOH, and DCM, in order to obtain accurate results for the other solvents the MP2 aug-cc-pVDZ level calculations should be used for CH3CN and CHCl3 solutions.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science and Literature, Balikesir University, Balıkesir, Turkey

    Sedat Karabulut & Hilmi Namli

  2. Interdisciplinary Nanotoxicity Center, Jackson State University, Jackson, MS, USA

    Jerzy Leszczynski

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  1. Sedat Karabulut
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  2. Hilmi Namli
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  3. Jerzy Leszczynski
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Correspondence to Sedat Karabulut.

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Karabulut, S., Namli, H. & Leszczynski, J. Detection of tautomer proportions of dimedone in solution: a new approach based on theoretical and FT-IR viewpoint. J Comput Aided Mol Des 27, 681–688 (2013). https://doi.org/10.1007/s10822-013-9669-z

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