Chemistry of Heterocyclic Compounds

, Volume 20, Issue 11, pp 1235–1240 | Cite as

Comparative analysis of the electronic structure of positional isomers: Indole-isoindole

  • V. A. Kovtunenko
  • Z. V. Voitenko
  • V. L. Sheptun
  • A. K. Tyltin
  • A. I. Chernega
  • Yu. T. Struchkov
  • F. S. Babichev
Article

Abstract

On the basis of an analysis of the canonical and localized molecular orbitals of indole and isoindole, calculated in the SCF and CNDO/2 approximations, as well as an x-ray crystallographic investigation of 2-methyl-isoindole, a comparison of the electronic structure of the positional isomers was made. The 10π-electronic system of isoindole is more integral than for indole: isoindole is a single 10π-electronic system with an appreciable localization of the bonds in the carbocyclic portion of the bicycle; the electronic structure of indole can be represented in a first approximation as the aggregate of three weakly interacting π-subsystems: the benzene ring, the double bond between the α- and β-carbon atoms, and the free electron pair of the nitrogen atom.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

Literature cited

  1. 1.
    J. S. Dewar, A. J. Harget, N. Trinajstic, S. D. Worley, Tetrahedron, 26, 4505 (1970).Google Scholar
  2. 2.
    O. E. Polansky and G. Derflinger, Monatsh., 92, 1114 (1961).Google Scholar
  3. 3.
    L. Klasinc, E. Pop, N. Trinajstic, and J. V. Knop, Tetrahedron, 28, Suppl. 13, 3465 (1972).Google Scholar
  4. 4.
    M. H. Palmer and S. M. F. Kennedy, J. Chem. Soc. Perkin Trans. II, No. 1, 81 (1976).Google Scholar
  5. 5.
    E. Chacko, J. Bornstein, and D. J. Sardella, J. Tetrahedron Lett., No. 13, 1095 (1977).Google Scholar
  6. 6.
    E. Chacko, J. Bornstein, and D. J. Sardella, J. Am. Chem. Soc., 99, 8248 (1977).Google Scholar
  7. 7.
    W. Rettig and J. Wirz, Helv. Chim. Acta, 59, 1054 (1976).Google Scholar
  8. 8.
    J. Fabian, J. Phys. Chem., 260, 82 (1979).Google Scholar
  9. 9.
    F. S. Babichev and V. A. Kovtunenko, The Chemistry of Isoindole [in Russian], Naukova Dumka, Kiev (1983).Google Scholar
  10. 10.
    Yu. A. Kruglyak, G. G. Dyadyusha, V. A. Kuprievich, L. M. Podol'skaya, and G. I. Kagan, Methods of Calculation of the Electronic Structure and Spectra of Molecules [in Russian], Naukova Dumka, Kiev (1969).Google Scholar
  11. 11.
    D. A. Zhogolev and V. B. Volkov, Methods, Algorithms, and Programs for Quantum Chemical Calculations of Molecules [in Russian], Naukova Dumka, Kiev (1976).Google Scholar
  12. 12.
    J. A. Pople and G. A. Segal, J. Chem. Phys., 44, 3289 (1966).Google Scholar
  13. 13.
    Molecular Structure by Diffraction Methods. A Specialist Periodical Report. The Chemical Society, Vol. 2 (1974).Google Scholar
  14. 14.
    A. Gordon and R. Ford, The Chemist's Companion, Wiley (1973).Google Scholar
  15. 15.
    A. I. Kitaigorodskii, P. M. Zorkii, and V. K. Bel'skii, Structure of Organic Matter. Data of Structural Investigations 1929–1970 [in Russian], Nauka, Moscow (1980).Google Scholar
  16. 16.
    A. F. Pozharskii, Khim. Geterotskikl. Soedin., No. 5, 723 (1977).Google Scholar
  17. 17.
    J. R. Platt, Systematics of the Electronic Spectra of Conjugated Molecules, Wiley, New York (1964).Google Scholar
  18. 18.
    R. Bonnett and R. F. C. Brown, Chem. Commn., No. 7, 393 (1972).Google Scholar
  19. 19.
    É. Sterns and K. Timmons, Electronic Absorption Spectroscopy in Organic Chemistry, St. Martin's Press (1970).Google Scholar
  20. 20.
    G. F. Bol'shakov, V. S. Vatago, and F. B. Bagrest, Ultraviolet Spectra of Heteroorganic Compounds [in Russian], Khimiya, Leningrad (1969).Google Scholar
  21. 21.
    V. I. Baranovskii, V. F. Brattsev, A. I. Panin, and V. M. Tret'yak, Methods of Calculation of the Electronic Structure of Atoms and Molecules [in Russian], M. G. Veselov, ed., Izd. LGU, Leningrad (1976).Google Scholar
  22. 22.
    A. T. Pilipenko, L. I. Savranskii, and V. A. Nikitina, Dokl. Akad. Nauk SSSR, 246, 625 (1979).Google Scholar
  23. 23.
    V. A. Kovtunenko, Z. V. Voitenko, A. N. Chernega, A. A. Espenbetov, M. Yu. Antipin, A. K. Tyltin, Yu. T. Struchkov, and F. S. Babichev, Ukr. Khim., 50, 988 (1984).Google Scholar
  24. 24.
    E. Corradi, P. Lazzaretti, and F. Taddei, Mol. Phys., 26, 41 (1973).Google Scholar
  25. 25.
    P. Crews, R. R. Kinter, and H. C. Padgett, J. Org. Chem., 38, 4391 (1973).Google Scholar

Copyright information

© Plenum Publishing Corporation 1985

Authors and Affiliations

  • V. A. Kovtunenko
    • 1
    • 2
  • Z. V. Voitenko
    • 1
    • 2
  • V. L. Sheptun
    • 1
    • 2
  • A. K. Tyltin
    • 1
    • 2
  • A. I. Chernega
    • 1
    • 2
  • Yu. T. Struchkov
    • 1
    • 2
  • F. S. Babichev
    • 1
    • 2
  1. 1.T. G. Shevchenko Kiev State UniversityKiev
  2. 2.A. N. Nesmeyanov Institute of Heteroorganic CompoundsMoscow

Personalised recommendations