Synthesis of Methyl Pyropheophorbide-a Substituted with Mono(di)-long Chain Alkyl Group at 3-Position

Abstract

From methyl pyropheophorbide-a (1), the aldehyde chlorin 2 was obtained by the protecton of ring-E and oxidation of vinyl group at 3-position. Grignard reaction with long chain alkyl magnesium bromide converted the formyl group into the acyl group. The hydroxyl group of sec-alcohol chlorin 3 was oxidized by mixed oxidizing agent consisting of tetrapropylammonium perruthenate and N-methylmorpholine N-oxide to generate 3-acyl pyropheophorbide-a derivative 4. The Grignard reaction of which with long chain alkyl magnesium bromide was carried out to yield tertiary alcohol chlorin 5 as nucleophilic adduct and chlorin 3 as reduced product. The following dehydration of alcohol chlorin 3 or 5 was performed in the dry benzene at reflux to form trans-form methyl pyropheophorbide-a substituted with mono- or di-long chain alkyl group at 3-position 6 or 7, respectively. The structures of all new compounds were characterized by elemental analysis, UV, IR and ¹H NMR spectra.

Key words: methyl pyropheophorbide-a, Grignard reaction, photodynamic therapy, chlorophyll derivative

Cite this article

WANG Jin-Jun*^,1,JI Jian-Ye²,JING Ji-Rong,LI Jia-Zhu
HAN Guang-Fan³,SHIM Young Key⁴. Synthesis of Methyl Pyropheophorbide-a Substituted with Mono(di)-long Chain Alkyl Group at 3-Position[J]. Chin. J. Org. Chem., 2006, 26(04): 470-476.

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3-位长链烷基双(单)取代焦脱镁叶绿酸-a甲酯的合成