Conformational analysis of o-allylphenol by density functional and IR spectroscopy methods

  • D. V. Berdyshev
  • V. P. Glazunov
  • V. L. Novikov
Article

The two-dimensional cyclic potential energy surfaces for internal rotation of the allyl substituent and its vinyl fragment in o-allylphenol (o-APh) depending on the OH group orientation relative to the allyl substituent were constructed by a B3LYP/6-31G method. It is shown that o-APh exists in the gas phase as a mixture of eight non-planar rotamers (A, B, C, D, E, F, G, and H) and their eight optical isomers (A 1, B 1, C 1, D 1, E 1, F 1, G 1, and H 1). An intramolecular H-bond (IHB) O–H...π occurs only in four rotamers (A, B, A 1, and B 1). The content of such rotamers in the gas phase is 47.2% (as calculated by the B3LYP/cc-pVTZ method). Taking into account the solvation effect in the polarizable continuum model (PCM) for a solution of o-APh in cyclohexane decreases the total content of rotamers with an IHB (A and B) to 37.7%. The ratio of rotamers with OH groups bonded by an IHB and with free OH groups that is predicted theoretically agrees with the value measured experimentally from IR spectra of o-APH in CCl4 solution.

Keywords

o-allylphenol quantum-chemical calculation density functional theory conformational analysis rotamers potential energy surface IR spectrum solvation effect 

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Copyright information

© Springer Science+Business Media, Inc. 2009

Authors and Affiliations

  • D. V. Berdyshev
    • 1
  • V. P. Glazunov
    • 1
  • V. L. Novikov
    • 1
  1. 1.Pacific Institute of Bioorganic ChemistryFar-Eastern Branch of the Russian Academy of SciencesVladivostokRussia

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