The Analytical Reduction of Porphyrins to Pyrroles

Autor: Chapman, R. A., Roomi, M. W., Morton, T. C., Krajcarski, D. T., MacDonald, S. F.
Zdroj: Canadian Journal of Chemistry; November 1971, Vol. 49 Issue: 21 p3544-3564, 21p
Abstrakt: When porphyrins or related pigments are reduced by HI–AcOH, their meso-substituents (R = H or alkyl) appear as α-CH2R groups in the resulting pyrroles. The identification of the pyrroles, as by g.l.p.c., defines and orders the meso-substituents flanking each pair of peripheral substituents in the porphyrin. If one meso-substituent differs from the others, all the substituents about the two adjacent pyrrole nuclei are then ordered.The pyrroles can be reductively alkylated in situ, and symmetry then reduces their number when the aldehyde used (R.CHO) corresponds to a bridge and its meso-substituent. This may simplify the pyrrole mixtures, identify meso-substituents, or make pyrroles distinguishable by g.l.p.c.The critical pyrrole – propionic acids are separable as methyl esters by g.l.p.c. Desoxophylloerythrin and pyrophaeophorbides (the latter first reduced with potassium borohydride) are reduced to cyclo-penteno-pyrroles which reveal the isocyclic rings and the 5-substituents. The r.r.t.'s of relevant pyrroles are reported.
Databáze: Supplemental Index