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

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Journal of Applied Spectroscopy Aims and scope

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.

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Authors and Affiliations

  1. Pacific Institute of Bioorganic Chemistry, Far-Eastern Branch of the Russian Academy of Sciences, 159 100-let Vladivostoku Ave., Vladivostok, 690022, Russia

    D. V. Berdyshev, V. P. Glazunov & V. L. Novikov

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  1. D. V. Berdyshev
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  2. V. P. Glazunov
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  3. V. L. Novikov
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Correspondence to V. P. Glazunov.

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Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 5, pp. 666–676, September–October, 2009.

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Berdyshev, D.V., Glazunov, V.P. & Novikov, V.L. Conformational analysis of o-allylphenol by density functional and IR spectroscopy methods. J Appl Spectrosc 76, 630–640 (2009). https://doi.org/10.1007/s10812-009-9258-z

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