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Spectroscopic detection of theendo-enol form of 2-acetylcyclopentane-1,3-dione

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According to vibrational spectroscopic data, in the gas phase at 280 °C and in crystals prepared by sublimation, 2-acetylcyclopentane-1,3-dione was established to exist not as trione 1 but as the enol-form 2 with an exo-cyclic C=C bond (v(C=C) = 1593 cm−1) and an intramolecular hydrogen bond. The enol 3 prepared by crystallization from CCl4 is also stabilized by an intramolecular H-bond but has anendo-cyclic C=C bond (v(C=C) = 1545 cm−1). In a trichloroethylene solution, both theexo- andendo-enol forms co-exist, and the percentage of the latter is ∼11 %. The frequencies in the vibrational spectra have been assigned using the normal coordinate calculation of2, 3, and their OD-analogs. The mechanism of tautomer transfer is discussed in terms of PMO theory.

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  1. 1.

    A. A. Akhrem and F.A. Lakhvich,IV Vsesoyus. Conf, on Chemistry of β-dikarbonyl Compounds. Abstracts of Papers, Zinatne, Riga, 1976, 11 (in Russian).

  2. 2.

    K. A. K. Ebraheem, S. T. Hamdi, and M. N. Khalaf,Can. J. Spectrosc., 1981,26, 225.

  3. 3.

    V. A. Shagun, V. F. Sidorkin, V. A. Usov, and M. G. Voronkov,I zv. Acad. Nauk USSR, Ser. Khim., 1981, 1747 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1981,30, 1417 (Engl. Transl.)].

  4. 4.

    V. Z. Kurbako, V. V. Gromak, V. G. Avakyan, and S. V. Rykov,Izy. Acad. Nauk USSR, Ser. Khim., 1991, 1358 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1991,40, 1199 (Engl. Transl.)].

  5. 5.

    S. Forsen, F. Merenyi, and M. Nilsson,Acta Chem. Scand., 1964,17, 1208.

  6. 6.

    H. C. Brown, J. H. Brewster, and H. Shechter,J. Am. Chem. Soc., 1954,76, 467.

  7. 7.

    V. G. Avakyan, V. V. Gromak, and V. Z. Kurbako,Izv. Acad. Nauk USSR, Ser. Khim., 1989, 2337 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1989,38, 2188 (Engl. Transl.)].

  8. 8.

    M. Yu. Antipin, M. V. Petrova, Ya. Ya. Pualin'sh, Yu. T. Struchkov, and E. Yu. Gudriniece,Izv. Acad. Nauk Latv. SSR, Ser. Khim., 1989, 102 (in Russian).

  9. 9.

    M. J. Nolte, P. S. Stayn, and P. L. Wessels,J. Chem. Soc.,Perkin Trans, 1, 1980, 1057.

  10. 10.

    F. Merenyi and M. Nilsson,Acta Chem. Scand., 1963,17, 1801.

  11. 11.

    A. V. Iogansen and M. Sh. Rosenberg,Zh. Prikl. Spectrosc., 1968,9, 1027 (in Russian).

  12. 12.

    L. A. Gribov and V. A. Dement'eyv,Metody i algoritmy vychislenii v teorii kolebatel'nykh spectrov [Methods and algorithms of calculations in the theory of vibrational spectra], Nauka, Mocsow, 1981 (in Russian).

  13. 13.

    L. A. Gribov, V. A. Dement'eyv, and O. V. Novoselova,Interpretirovannye kolebatel'nye spectry uglevodorodov s izolirovannymi i sopryazhennymi kratnymi svyazyami [Interpreted vibrational spectra of hydrocarbons with isolated and conjugated multiple bonds], Nauka, Mocsow, 1987 (in Russian).

  14. 14.

    M. E. El'yashberg, M. Yu. Karasev, V. A. Dement'eyv, and L. A. Gribov,Interpretirovannye kolebatel'nye spectry uglevodorodov — proizvodnykh tsiklopentana i tsiklogeksana [Interpreted vibrational spectra of hydrocarbons — derivatives of cyclopentane and cyclohexane], Nauka, Mocsow, 1988 (in Russian).

  15. 15.

    Z. Smith, E. B. Wilson, and R. W. Duerst,Spectrochim. Acta, 1983,39A, 1117.

  16. 16.

    L. Bellamy,Infrared Spectra of Complex Molecules, Wiley, New York, 1954.

  17. 17.

    T. Yamaguchi, K. Saito, T. Tsujimoto, and H. Yuki,J. Heterocycl. Chem., 1976,13, 533.

  18. 18.

    A. Gordon and R. Ford,The Chemist's Companion, Wiley-Interscience, New York-London-Sidney-Toronto, 1972.

  19. 19.

    G. Klopman,Chemical Reactivity and Reaction Paths, Wiley, New York, 1974.

  20. 20.

    G. Klopman,J. Am. Chem. Soc., 1968,90, 223.

  21. 21.

    V. G. Dashevski,Konformatsii organicheskikh molekul [Conformations of Organic Molecules], Khimiya, Mocsow, 1974 (in Russian).

  22. 22.

    E. Lepinsh, M. V. Petrova, E. Gudriniece, J. Paulinsh, and S. L. Kuznetsov,Magn. Reson. Chem., 1989,27, 907.

  23. 23.

    P. Piaggio and M. Rui,J. Mol. Struct., 1981,75, 171.

  24. 24.

    E. A. Borisov, T. S. Khlebnikova, D. B. Rubinov, F. A. Lakhvich,Zh. Org. Khim., 1992,28, 1306 [J. Org. Chem. USSR, 1992,28 (Engl. Transl.)].

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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 57–62, January, 1994.

The authors are grateful to professor J. G. Ramos (Madrid Institute of Optics) for making it possible to record the far IR and Raman spectra in his laboratory, to Dr. V. Z. Kurbako for the registration of spectra and its discussion, and to Dr. N. A. Kubasova for recording the Raman spectra with a Coderg Ar-300 instrument.

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Avakyan, V.G., Gromak, V.V. & Yatsenko, A.Y. Spectroscopic detection of theendo-enol form of 2-acetylcyclopentane-1,3-dione. Russ Chem Bull 43, 50–56 (1994). https://doi.org/10.1007/BF00699134

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Key words

  • tautomerism of β,β'-tricarbonyl compounds
  • exo- andendo-enol forms of 2-acetylcyclopentane-1,3-dione