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Zur Chemie der Pyrrolpigmente, 63. Mitt.

On the chemistry of pyrrole pigments LXIII: Phytochrome model studies: The system 2,3-dihydrobilatriene—Hexamethylphosphoric acid triamide as a model for stretched chromophores

Phytochrommodellstudien: Das System 2,3-Dihydrobilatrien—Hexamethylphosphorsäuretriamid als Modell für gestreckte Chromophore

  • Organische Chemie And Biochemie
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Monatshefte für Chemie / Chemical Monthly Aims and scope Submit manuscript

Abstract

Using hexamethylphosphoric acid triamide (HMPT) as solvent for bilatrienesabc and mainly for 2,3-dihydrobilatrienes-abc (which serve as the most suitable models for the biliproteid chromophores) a small hypsochromic shift and a dramatic change of the relative intensities of short and long wavelength absorption bands, as compared to solutions in CCl4, is observed. Applying NMR-spectroscopic techniques (15N-,13C-,1H-) a predominance of the (4Z,9E,15Z) diastereomer forming a 5syn-, 10anti-, 14syn-periplanar orclinal conformation is deduced. The stabilisation of this configuration and conformation arises from strong hydrogen bonds between the acidic protons of the bilins andHMPT. Interactions of this kind seem to be the main source of energy to stretch the otherwise coiled bilin chromophore of (4Z,9Z,15Z)-5sp,10sp,14sp geometry. Stretched systems of the type bilin-HMPT may serve as a valuable model for the natural biliproteides.

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Authors and Affiliations

  1. Institut für Analytische, Organische und Physikalische Chemie, Johannes-Kepler-Universität, A-4040, Linz, Österreich

    Heinz Falk, Norbert Müller & Silvia Wansch

Authors
  1. Heinz Falk
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  2. Norbert Müller
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  3. Silvia Wansch
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Additional information

Herrn Prof. Dr.A. Eschenmoser zum 60. Geburtstag gewidmet.116, 1065 (1985).

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Falk, H., Müller, N. & Wansch, S. Zur Chemie der Pyrrolpigmente, 63. Mitt.. Monatsh Chem 116, 1087–1097 (1985). https://doi.org/10.1007/BF00809199

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  • DOI: https://doi.org/10.1007/BF00809199

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