Air Oxidation and Rearrangement Reactions of Methyl(pyro)-pheophorbide-a in the Presence of Lithium Hy-droxide

Abstract

In the presence of lithium hydroxide, air oxidation and rearrangement reactions of methyl pheo- phorbide-a (1a) followed by acidification with hydrochloric acid and methylation with diazomethane to give a mixture including purpurin-7 trimethyl ester (2), purpurin-18 methyl ester (3), chlorine-p₆ trimethyl ester (4), geoporphyrin derivatives (5) and 3-epoxyvinyl-3-devinylpurpurin-18 ester (6) were performed. Methyl pyropheophorbide-a (1b) was oxidized in the same reaction as chlorin 1a followed by chromatography isola- tion to obtain methyl 13²-oxopyropheophorbide-a (7), 15-formylpurpurin-5 dimehyl ester (8), purpurin-18 methyl ester (3) and 3-epoxyvinyl-3-devinylpurpurin-18 ester (6), respectively. The structures of new chlorophyll derivatives 5, 6 and 8 were characterized by UV, IR, ¹H NMR spectra and elemental analysis. The possible mecha-nisms for the air oxidation and rearrangement reaction were tentatively proposed.

Key words: methyl(pyro)pheophorbide-a, air oxidation, rearrangement reaction, photodynamic therapy, chlorophyll-a

Cite this article

LI Jia-Zhu^b,c, LIU Wan-Hui^c, LI Fu-Guo^b, WANG Jin-Jun,b
SUO You-Rui^a, LIU Yong-Jun*^,a. Air Oxidation and Rearrangement Reactions of Methyl(pyro)-pheophorbide-a in the Presence of Lithium Hy-droxide[J]. Chin. J. Org. Chem., 2007, 27(12): 1594-1599.

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氢氧化锂存在下(焦)脱镁叶绿酸-a甲酯的空气重排反应