Alkynylation of Pyropheophorbide-a and Synthesis of Chylorophyllous Chlorin Derivatives

doi:10.6023/cjoc201205002

Chin. J. Org. Chem. ›› 2012, Vol. 32 ›› Issue (10): 1936-1943.DOI: 10.6023/cjoc201205002 Previous Articles Next Articles

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焦脱镁叶绿酸的炔化反应及其叶绿素类二氢卟吩的合成

殷军港^a, 王振^a, 杨泽^a, 金英学^b, 王进军^a,c

a 烟台大学化学化工学院烟台 264005;
b 哈尔滨师范大学化学化工学院哈尔滨 150025;
c 山东省黄金工程技术研究中心(工业应用) 烟台 264005

收稿日期:2012-05-02 修回日期:2012-05-29 发布日期:2012-06-05
通讯作者: 王进军 E-mail:wjj1955@163.com
基金资助:
国家自然科学基金(No. 20972036 )和山东省自然科学基金(No. Y2008B49)资助项目.

Alkynylation of Pyropheophorbide-a and Synthesis of Chylorophyllous Chlorin Derivatives

Yin Jungang^a, Wang Zen^a, Yang Ze^a, Jin Yingxue^b, Wang Jinjun^a,c

a College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005;
b College of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025;
c Shandong Applied Research Centre of Gold Nanotechnology (Au-SDARC), Yantai 264005

Received:2012-05-02 Revised:2012-05-29 Published:2012-06-05
Supported by:
Project supported by the National Natural Science Foundations of China (No. 20972036) and the Natural Science Foundation of Shandong Province of China (No. Y2008B49).

Methyl pyropheophorbide-a was used as starting material and converted into 3-formyl or 3-acetyl substituted and E-ring protected reactive precursors. The Grignard reactions of these carbonyl groups introduced alkynyl groups at 3-position to build the tert-alcohol or sec-alcohol structures. Further dehydrations and oxidations produced terminal eneyne and ketyne substituted chlorins, respectively. The pyropheophorbide-a with long chain alkyl group at 3-position was obtained by Grignard reaction with decyl magnesium bromide, protection for E-ring and oxidation of C(3)-hydroxyl group from 3-formylpyropheo- phorbide-a, converted into chlorin containing eneyne moiety in chain by acid-catalyzed dehydration. The structures of all new chlorin derivatives were characterized by elemental analysis, UV, IR and ¹H NMR spectra. The possible mechanisms about corresponding reactions were tentatively proposed.

Key words: chlorophyll-a, pyropheophorbide, chlorin, alkynylation, chemical modification

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Yin Jungang, Wang Zen, Yang Ze, Jin Yingxue, Wang Jinjun. Alkynylation of Pyropheophorbide-a and Synthesis of Chylorophyllous Chlorin Derivatives[J]. Chin. J. Org. Chem., 2012, 32(10): 1936-1943.

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焦脱镁叶绿酸的炔化反应及其叶绿素类二氢卟吩的合成

Alkynylation of Pyropheophorbide-a and Synthesis of Chylorophyllous Chlorin Derivatives

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