Synthesis of Cyanided Chlorophyllous Chlorin Derivatives and Study on Their Photodynamic Activities

doi:10.6023/cjoc201506037

Chin. J. Org. Chem. ›› 2016, Vol. 36 ›› Issue (3): 580-589.DOI: 10.6023/cjoc201506037 Previous Articles Next Articles

Articles

氰化叶绿素类二氢卟吩衍生物的合成及其光动力活性的研究

高娜^a, 王振^b, 武进^b, 刘超^b, 王进军^a,b

a 烟台大学文经学院食品与生物工程系烟台 264005;
b 烟台大学化学化工学院烟台 264005

收稿日期:2015-06-30 修回日期:2015-11-16 发布日期:2015-11-16
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. 21272048)和山东省黄金工程技术研究中心(2011年度)资助项目.

Synthesis of Cyanided Chlorophyllous Chlorin Derivatives and Study on Their Photodynamic Activities

Gao Na^a, Wang Zhen^b, Wu Jin^b, Liu Chao^b, Wang Jinjun^a,b

a Department of Food & Biological Engineering, Wenjing College, Yantai University, Yantai 264005;
b College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005

Received:2015-06-30 Revised:2015-11-16 Published:2015-11-16
Supported by:
Project supported by the National Natural Science Foundations of China (No. 21272048) and the Project of Shandong Applied Reasearch Centre of Gold Nanotechnology (2011).

1. Synthesis of Cyanided Chlorophyllous Chlorin Derivatives and Study on Their Photodynamic Activities.PDF(742KB)

Abstract

Pyropheophorbide-a methyl ester was used as a starting material, and its oxygenations were carried out by thaillum nitrate and air as oxidizing agent to introduce the formyl group and the formylmethyl group at 3-, 12-or 15-postion of chlorin periphery, respectively. After oximation these aldehyde groups were converted into cyano group under the reaction mediated from N,N-dimethylformamide and 2,4,6-trichloro-1,3,5-triazine. Dicyanomethylene moiety was established by Knoevenagel reaction of malononitrile with formyl group and 13¹-carbounyl group on the exocyclic ring. Mulcyano-substitutions on the chromophore were accomplished by further structure modifications. A series of unreported chlorins related to chlorophyll substituted with cyano-group were synthesized making use of cyanation at different positions on the periphery of chlorophyll degradation products. Their chemical structures were characterized by elemental analysis, UV, IR and ¹H NMR spectra. The reaction mechanisms on the cyanation for the chlorophyllous chlorins were discussed and in vitro photodynamic activities of some new compounds were determined.

Key words: chlorophyll-a, chlorin, chemical modification, cyanation reaction, photodynamic activity

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Gao Na, Wang Zhen, Wu Jin, Liu Chao, Wang Jinjun. Synthesis of Cyanided Chlorophyllous Chlorin Derivatives and Study on Their Photodynamic Activities[J]. Chin. J. Org. Chem., 2016, 36(3): 580-589.

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氰化叶绿素类二氢卟吩衍生物的合成及其光动力活性的研究

Synthesis of Cyanided Chlorophyllous Chlorin Derivatives and Study on Their Photodynamic Activities

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