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THE SYNTHESIS AND CHARACTERIZATION OF PORPHYRINS AND METALLOPORPHYRINS WITH ELECTRON-WITHDRAWING PYRROLE SUBSTITUENTS
Abstract
N-Benzoylpyrrole was synthesized by reaction of 2,5-dimethoxytetrahydrofuran with benzamide. A retro Diels-Alder reaction of the product with dimethyl acetylenedicarboxylate produced dimethyl-N-benzoyl-3,4-pyrrole dicarboxylate. Hydrolysis of the retro Diels-Alder product lead to 3,4-pyrroledicarboxylic acid. Fluorination of this acid pyrrole with sulfur tetrafluoride in the presence of hydrogen fluoride produced 3,4-pyrrolediacylfluoride. When the diacid pyrrole was reacted with oxalyl chloride 3,4-pyrroledicarbonyl chloride was produced. Amination of pyrrolecarbonyl chloride with either dimethyl or diethylamine led to two new 3,4-bis-(dialkylformamide)-pyrroles. Treating 3-carbomethoxy-4-pyrrolecarboxylic acid with diethylamine in a similar manner produced a new 3-carbomethoxy-4-bis-(diethylformamide)-pyrrole. Condensation of 3,4-bis-(diethylformamide)-pyrrole with formaldehyde in the presence of hydrobromic acid in ethanol led to a novel, highly soluble 1,2,3,4,5,6,7,8-octa-bis-(diethylformamide)-porphyrin in reasonable yield. Metalation of this new porphyrin with metal salts in N,N-dimethylformamide produced metalloporphyrins. When the cobalt porphyrin was dissolved in acetone and dry air bubbled through the solution for 50 hours, the presumed product was a dioxygen adduct. When dry nitrogen was passed for 5 hours through a benzene solution of this dioxygen adduct, the product was the original cobalt porphyrin. Bubbling dry air for 150 hours through an acetone solution of the oxygen-free cobalt porphyrin led irreversibly to what is hypothesized to be (mu)-oxo-cobalt porphyrin. The dioxygen adduct in acetone solution exposed to uv/vis light for only 2-3 minutes, gave the same (mu)-oxo-cobalt porphyrin. All the cobalt porphyrin species were characterized by uv/vis and esr spectroscopy.
Subject Area
Chemistry
Recommended Citation
SHIRAZI, ATAOLLAH, "THE SYNTHESIS AND CHARACTERIZATION OF PORPHYRINS AND METALLOPORPHYRINS WITH ELECTRON-WITHDRAWING PYRROLE SUBSTITUENTS" (1981). ETD collection for University of Nebraska-Lincoln. AAI8118181.
https://digitalcommons.unl.edu/dissertations/AAI8118181