Monatshefte für Chemie - Chemical Monthly

, Volume 109, Issue 6, pp 1429–1449 | Cite as

Beiträge zur Chemie der Pyrrolpigmente, 24. Mitt. Über die Beziehung zwischen Lichtabsorption und Struktur von Bilatrienen-abc

  • Heinz Falk
  • Günther Höllbacher
Organische Chemie und Biochemie

On the chemistry of pyrrole pigments, XXIV.: The correlation of light absorption and structure in the bilatrienes-abc

Abstract

Using the recently established solution structure of a bilatriene-abc derivative the parameter set of thePPP-SCF-LCAO-MO-Cl model was refined. The general trend, that molecular configuration itself does not so much determine the absorption spectra as was deduced by investigation of partial bile pigment structures, was confirmed for the bilatrienes-abc. Instead, the configuration at a particular double bond induces a certain torsional angle at the adjacent single bond which leads to dramatic spectral changes on isomerization of this double bond. Isomerization without this torsional effect brings about different relative intensities of the two main spectral bands. Comparing measured spectra of several bilatrienes-abc and calculated spectra a helicalsyn, syn, syn-conformation with three torsional angles at the methine fragments of appr. 20° was deduced for systems with (Z, Z, Z)-configuration. For a recently prepared (E, Z, Z)-derivative a nearly helicalsyn, syn, syn-conformation with torsional angles of 40°, 20° and 20° at the methine single bonds is the most probable.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

Literatur

  1. 2.
    T. K. With, Bile Pigments, New York: Academic Press. 1968.Google Scholar
  2. 3.
    R. K. Clayton, Light and Living Matter, Bd. 2. New York: McGraw-Hill. 1971.Google Scholar
  3. 4.
    G. Blauer, Struct. Bonding18, 69 (1974).CrossRefGoogle Scholar
  4. 5.
    M. J. Burke, D. C. Pratt undA. Moscowitz, Biochemistry11, 4025 (1972).CrossRefGoogle Scholar
  5. 6.
    H. Suzuki, T. Sugimoto undK. Nakachi, J. Phys. Soc. Jap.34, 1045 (1973);H. Suzuki, T. Sugimoto undK. Ishikawa, J. Phys. Soc. Jap.38, 1110 (1975);T. Sugimoto, K. Ishikawa undH. Suzuki, J. Phys. Soc. Jap.40, 258 (1976).CrossRefGoogle Scholar
  6. 7.
    J.-H. Fuhrhop, A. Salek, J. Subramanian, C. Mengersen undS. Besecke, Ann. Chem.1975, 1131.Google Scholar
  7. 8.
    G. Blauer undG. Wagnière, J. Amer. Chem. Soc.97, 1949 (1975).CrossRefGoogle Scholar
  8. 9.
    G. Wagnière undG. Blauer, J. Amer. Chem. Soc.98, 7806 (1976).CrossRefGoogle Scholar
  9. 10.
    Q. Chae undP. S. Song, J. Amer. Chem. Soc.97, 4176 (1975).CrossRefGoogle Scholar
  10. 11.
    H. Falk undO. Hofer, Mh. Chem.106, 97 (1975).Google Scholar
  11. 12.
    H. Falk undO. Hofer, Mh. Chem.106, 115 (1975).Google Scholar
  12. 13.
    H. Falk, K. Grubmayr, O. Hofer undF. Neufingerl, Mh. Chem.106, 991 (1975).Google Scholar
  13. 14.
    H. Falk, K. Grubmayr, G. Höllbacher, O. Hofer, A. Leodolter, F. Neufingerl undJ. M. Ribó, Mh. Chem.108, 1113 (1977).Google Scholar
  14. 15a).
    H. Falk, S. Gergely, K. Grubmayr undO. Hofer, Z. Naturforsch.32b, 299 (1977).Google Scholar
  15. 15b).
    Siehe das UV-VIS-Spektrum inJ. V. Bonfiglio, R. Bonnett, M. B. Hursthouse, K. M. A. Malik undS. C. Naithani, J. L. S. Chem. Commun.1977, 829.Google Scholar
  16. 16.
    J. E. Bloor undN. Brearley, Can. J. Chem.43, 1761 (1965). QCPE-Programm Nr. 71/2.CrossRefGoogle Scholar
  17. 17.
    H. Falk, S. Gergely, K. Grubmayr undO. Hofer, Ann. Chem.1977, 565.Google Scholar
  18. 18.
    H. Falk, S. Gergely undO. Hofer, Mh. Chem.105, 1004 (1974).Google Scholar
  19. 19.
    H. Falk, K. Grubmayr, U. Herzig undO. Hofer, Tetrahedron Lett.1975, 559.Google Scholar
  20. 20.
    R. Bonnett, M. B. Hursthouse undS. Neidle, J. Chem. Soc., Perkin II,1972, 1335;D. L. Cullen, P. S. Black, E. F. Meyer, D. A. Lightner, G. B. Quistad undC. S. Pak, Tetrahedron Lett.33, 477 (1977).Google Scholar
  21. 21.
    R. Bonnett, J. E. Davis undM. B. Hursthouse, Nature262, 326 (1976);W. S. Sheldrick, J. Chem. Soc. Perkin II,1976, 1457.CrossRefGoogle Scholar
  22. 22.
    H. Falk undK. Grubmay, Angew. Chem.89, 487 (1977).CrossRefGoogle Scholar
  23. 23.
    H. Scheer undW. Kufer, Z. Naturforsch32c, 513 (1977).Google Scholar
  24. 24.
    H. Falk undO. Hofer, Mh. Chem.105, 995 (1974).Google Scholar
  25. 25.
    H. Falk undK. Grubmayr, Mh. Chem.108 625 (1977).Google Scholar
  26. 26.
    R. Bonnett undA. F. McDonagh, Chem. Commun.1970, 238.Google Scholar
  27. 27.
    S. Grombein, W. Rüdiger undH. Zimmermann, Hoppe Seyler's Z. Physiol. Chem.356, 1709 (1975).CrossRefGoogle Scholar
  28. 28.
    J. A. S. Cavaleiro undK. M. Smith, J. Chem. Soc., Perkin I,1973, 2149.Google Scholar
  29. 29.
    H. Falk, O. Hofer undH. Lehner, Mh. Chem.105, 169 (1974).Google Scholar
  30. 30.
    Lit.30:H. Falk, K. Grubmayr, O. Hofer, F. Neufingerl undJ. M. Ribó, Mh. Chem.107, 831 (1976);H. Falk, K. Grubmayr undT. Schlederer, Mh. Chem.109, 1191 (1978).Google Scholar
  31. 31.
    H. Falk, K. Grubmayr, K. Thirring undN. Gurker, Mh. Chem.109, 1183 (1978).Google Scholar
  32. 32.
    S.z. B.E. Heilbronner undH. Bock, Das HMO-Modell und seine Anwendung, I, 253. Weinheim: Verlag Chemie. 1968.Google Scholar
  33. 33.
    J.-H. Fuhrhop undJ. Subramanian, Phil. Trans. R. Soc. London,B273, 335 (1976).CrossRefGoogle Scholar
  34. 34.
    K. Fukui, T. Yonezawa undC. Nagata, J. Chem. Phys.26, 831 (1957).CrossRefGoogle Scholar
  35. 35.
    J. H. Fuhrhop undD. Mauzerall, Photochem. Photobiol.13, 453 (1971);A. W. Nichol undP. B. Morell, Biochim. Biophys. A.177, 599 (1969);F. Eivazi, W. M. Lewis undK. M. Smith, Tetrahedron Lett.1977, 3083; M.F. Hudson undK. M. Smith, Chem. Soc. Rev.4, 363 (1975).CrossRefGoogle Scholar
  36. 36.
    H. Falk undT. Schlederer, Mh. Chem.109, 1013 (1978).Google Scholar
  37. 37.
    H. Falk undK. Grubmayr, Synthesis,1977, 614.Google Scholar
  38. 38.
    H. Plieninger undA. Gossauer, Synth., Purific. and Charact. of the Bile Pigments and Rel. Compounds, in: The Prophyrins (D. Dolphin, Hrsg.), im Druck; wir danken Herrn Prof.Gossauer für die Überlassung eines Vorabdruckes sehr herzlich; s.H. Plieninger, F. El Barkawi, K. Ehl, R. Kohler undA. F. McDonagh, Ann. Chem.758, 195 (1972).Google Scholar

Copyright information

© Springer-Verlag 1978

Authors and Affiliations

  • Heinz Falk
    • 1
  • Günther Höllbacher
    • 1
  1. 1.Institut für Organische ChemieUniversität WienWienÖsterreich

Personalised recommendations