An alternative synthesis of benziporphyrins starting from isophthaloyl chloride

Abstract

An alternative route to benziporphyrins has been developed. Reaction of an [Formula: see text]-unsubstituted pyrrole ethyl ester with isophthaloyl chloride in the presence of aluminum chloride afforded a diketone that underwent selective reduction with diborane to give a benzitripyrrane. Cleavage of the ethyl esters with sodium hydroxide in refluxing ethylene glycol, followed by acid catalyzed condensation with a pyrrole dialdehyde and oxidation with DDQ, generated the targeted benziporphyrin product. Spectrophotometric titration of the benziporphyrin with trifluoroacetic acid (TFA) demonstrated the sequential formation of mono- and dicationic species. At lower dilutions, the free base benziporphyrin showed unusually strong [Formula: see text] coupling between two adjacent methyl substituents, indicating that the connecting unit has substantial olefinic characteristics.