Alfred Leodolter

Beiträge zur Chemie der Pyrrolpigmente, 18. Mitt.: Pyrromethenone—Partialstrukturen von Gallenpigmenten: Struktur und Eigenschaften in Lösung

Depending on solvent polarity and concentration a monomer—dimer equilibrium for pyrromethenones was deduced by means of absorption and fluorescence spectroscopy and measurement of a colligative property. The monomer could be characterized as asyn-(Z) form with a dihedral angle at the methine single bond of about fourty degrees using the lanthanide shift technique and nuclearOverhauser effect studies. Two types of dimer geometry with differing bond strengths were found by comparingPPP calculation results with the measured absorption spectra and the liquid crystal induced circular dichroism.The (Z) isomers can be transformed to the corresponding (E) isomers by means of a photoreaction. The latter is thermally stable but rather sensitive against oxygen, light and protons, an effect which varies strongly with the substitution pattern of the pyrrole fragment thus enabling isolation in certain cases only.

Beiträge zur Chemie der Pyrrolpigmente, 19. Mitt.: Die elektrochemische Oxidation von Pyrromethenonen und Pyrromethenen (Gallenpigment-Partialstrukturen)

The electrochemical oxidation of arylmethylene-pyrrolinones, pyrromethenones and pyrromethenes as representative bile pigment partial structure models was investigated by means of a rotating disc platinum electrode using acetonitrile as the solvent. Two different oxidation reactions were found. The first reaction being a reversible one-electron oxidation with compounds of the arylmethylene-pyrrolinone series and pyrromethenones which are unsubstituted in position 5 of the pyrrole ring. A two step reaction (the first one reversible, the second irreversible) on the other hand was found to be typical for pyrromethenones bearing a methyl group in this position.Through protonation the first step is at a higher potential, whereas the second one is lowered and becomes reversible. The resulting oxidation pattern can be interpreted analogous to the oxidation of hydroquinones in aprotic solvents.The geometrical isomers of a pyrromethenone were oxidized at appr. the same potential, but there is a strong dependence of the potential of the first oxidation step on the substitution: a higher degree of alkylation favours oxidation by lowering the oxidation potential.

Beiträge zur Chemie der Pyrrolpigmente, 20. Mitt.: Untersuchungen über das Deprotonierungsgleichgewicht und die Bildung von Metallkomplexen von Gallenpigment-Partialstrukturen

By spectrophotometric measurements in the systemDMSO/H2O/Me4NOH pKa-values for several model compounds representing bile pigment partial structures were established. The acidic protons of pyrrole and lactame type nitrogen atoms are removed by bases governed by the electronic properties of the substituents on these ring systems. The pKa-values for both types lie in the same region. In the pyrromethenones the lower one corresponds to the lactame type NH as was deduced by comparison with specifically methylated derivatives.The complexation of these ligands is determined by the possibility of removing an acidic proton and achieving a chelate structure by means of an adjacent pyrrolinone type nitrogen atom. Complexes are favoured in the series pyrromethenes > lactim ethers > pyrromethenones. With the latter there are two possibilities: one observed with BF2-chelation where the lactime form becomes stabilized, the other one with zink where both acidic centers are involved in the bonding.

Beiträge zur Chemie der Pyrrolpigmente, 14. Mitt. Interkonversionsprozesse bei Arylmethylidenpyrrolinonen; ein Spezialfall atropisomerer, sterisch gehinderter Styrole

Starting from a chiral substituted benzaldehyde diastereomeric arylmethylidenepyrrolinones were accessible. The geometrical structures of the corresponding isomers were investigated by lanthanide ion induced shift technique and UV spectroscopy. By equilibration studies, D-NMR measurements and kinetic data a complete picture of the various ground state enthalpy differences as well as the activation energies of the transition paths was gained.The results are in accord with the barriers determined for two simple model derivatives belonging to the class of atropisomeric sterically hindered styrenes.

Beiträge zur chemie der Pyrrolpigmente, 10. Mitt.: Elektronenspektrometrische Untersuchungen über die Struktur von Quadratsäurederivaten

The structure of squaric acid derivatives was investigated on the basis of the PPP—SCF—LCAO—MO—CI method utilizing the π-electron densities and bond orders. The parameters used in the calculations were modified to fit the experimental data for representative compounds. The data were obtained by X-ray photoelectron spectrometry and electron absorption spectroscopy (including the polarization of the bands as determined by liquid crystal induced circular dichroism measurements).