Title

New Syntheses and Reactions of Some Halogenated Porphyrins

Document Type

Article

Publication Date

11-1-1989

Abstract

Efficient syntheses of 2,4-dibromo- and 2,4-diiododeuteroporphyrin IX have been carried out by treating zinc(II) 2,4-bis(chloromercurio)deuteroporphyrin IX dimethyl ester (2) with bromine or iodine. Unavoidable meso-chlorination occurs when 2 is treated with chlorine and with other free-radical chlorinating agents. Regioselective meso-chlorination and peripheral (β) bromination are shown to occur from brief treatment of copper(II) deuteroporphyrin IX or β-unsubstituted a,c-biladienes with the corresponding copper(II) halide in refluxing dimethylformamide. Protoporphyrin IX has been synthesized by vinylation of 2 via ethylene/LiPdCl3(35% yield), with vinyl bromide and Wilkinson's catalyst (63%), or from 2,4-dibromodeuteroporphyrin IX with ethenyl-tributylstannane/(Ph3P)4Pd0(85%). © 1989, American Chemical Society. All rights reserved.

Publication Source (Journal or Book title)

Journal of Organic Chemistry

First Page

5567

Last Page

5574

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