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Concerning the acidity and hydrogen bonding of hydroxyphenanthroperylene quinones like fringelite D, hypericin, and stentorin

Zu Acidität und Wasserstoffbrückenbindung von Hydroxyphenanthroperylenchinonen wie Fringelit D, Hypericin und Stentorin

  • Anorganische Und Physikalische Chemie
  • Published:
Monatshefte für Chemie / Chemical Monthly Aims and scope Submit manuscript

Summary

The strongly enhanced acidity of the bay hydroxyl group as compared to the respectiveperi hydroxyl groups of fringelite D, hypericin, and stentorin could be rationalized on the basis of a vinylogous carboxylic acid and was nicely corroborated by semiempirical calculations of the AM1 type. Experimental data obtained from several independent experimental methods, like polarized absorption spectroscopy, hole burning, and isotope effects, as well as from semiempirical AM1 and 6–31G levelab initio calculations conclusively pointed to dissymmetrical hydrogen bonding systems in both theperi andbay regions of the correspondingbay phenolate ions.

Zusammenfassung

Die stark erhöhte Acidität der bay-Hydroxylgruppen gegenüber jener derperi-Hydroxylgruppen von Fringelit D, Hypericin und Stentorin läßt sich auf der Basis einer vinylogen Carbonsäure verstehen und wurde auch durch semiempirische Rechnungen vom AM1-Typ erhärtet. Daten aus unabhängigen Experimenten wie Polarisationsspektroskopie, Lochbrennen und Isotopeneffekte sowie semiempirische AM1- undab initio-Rechnungen auf 6–31G Niveau belegen ein unsymmetrisches Wasserstoffbrückenbindungssystem sowohl für denperi-als auch denbay-Bereich der entsprechendenbay-Phenolationen.

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Authors and Affiliations

  1. Institut für Chemie, Johannes Kepler Universität, A-4040, Linz, Austria

    C. Etzlstorfer, H. Falk, E. Mayr & S. Schwarzinger

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  1. C. Etzlstorfer
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  2. H. Falk
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  3. E. Mayr
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  4. S. Schwarzinger
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Etzlstorfer, C., Falk, H., Mayr, E. et al. Concerning the acidity and hydrogen bonding of hydroxyphenanthroperylene quinones like fringelite D, hypericin, and stentorin. Monatsh Chem 127, 1229–1237 (1996). https://doi.org/10.1007/BF00807789

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  • DOI: https://doi.org/10.1007/BF00807789

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