Modification of C(3)-Vinyl Group and Synthesis of Oxygenic Group-Substituted Chorophyll-a Derivatives

Chin. J. Org. Chem. ›› 2011, Vol. 31 ›› Issue (01): 68-74. Previous Articles Next Articles

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C(3)-乙烯基的化学修饰与含氧基团取代的叶绿素-a衍生物的合成

王进军*^{,1,2，李付国²，李韵伟²}

(¹烟台大学化学生物理工学院烟台 264005)
(²烟台大学药学院烟台 264005)

收稿日期:2010-03-02 修回日期:2010-07-13 发布日期:2010-08-12
通讯作者: 王进军 E-mail:wjj1955@163.com
基金资助:
国家科技部中匈政府间合作项目;山东省自然科学基资助项目

Modification of C(3)-Vinyl Group and Synthesis of Oxygenic Group-Substituted Chorophyll-a Derivatives

Wang Jinjun*^{,1,2 Li Fuguo² Li Yun-wei²}

(¹ Science and Engineering College of Chemistry and Biology, Yantai University, Yantai 264005)
(²College of Pharmacy, Yantai University, Yantai 264005)

Received:2010-03-02 Revised:2010-07-13 Published:2010-08-12

Abstract

The vinyl group at 3-position of methyl pyropheophorbide-a, used as starting material, was converted into hydroxyethyl, bromoethyl, dihydroxyethyl, dibromoethyl and bromo-hydroxyethyl groups by addition and oxidation reactions. The multi-keto groups-substituted chlorin derivatives were obtained by oxidations with dimethyl sulfoxide/acetic anhydride or tetrappropylammonium perruthenate/N-methylmor- pholine N-oxide as a mixing oxidant. The nucleophilic substitution of the mono-hydroxyl group as a leaving group with active methlene derivatives produced many unexpected processes to give corresponding keto-substituted chlorin derivatives. The structures of new chlorophyll derivatives were characterized by UV, IR, ¹H NMR spectra and elemental analysis. The possible mechanisms about corresponding oxidation, substitution and rearrangement reactions were tentatively proposed.

Key words: chlorophyll-a, methyl pyropheophorbide-a, chlorin derivative, chemical modification, chemical mechanism, photodynamic therapy (PDT)

Cite this article

WANG Jin-Jun, LI Fu-Guo, LI Yun-Wei. Modification of C(3)-Vinyl Group and Synthesis of Oxygenic Group-Substituted Chorophyll-a Derivatives[J]. Chin. J. Org. Chem., 2011, 31(01): 68-74.

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[1]	Zhang Zhu, Li Jiazhu, Zhang Shanguo, Wang Zhen, Wang Jinjun. Heterocyclization for the Structures on the Periphery of Py-ropheophorbide and Synthesis of Chlorophyll Derivatives [J]. Chin. J. Org. Chem., 2018, 38(12): 3250-3259.
[2]	Zhang Zhu, Xu Xisen, Li Yanlong, Li Jiazhu, Wang Jinjun. Rearrangement Reactions of Pyropheophorbide with Diazoalkane and Synthesis of Chlorophyll Derivatives [J]. Chin. J. Org. Chem., 2018, 38(11): 2993-3001.
[3]	Jiang Qiyong, Zhang Zhu, Liu Yang, Yao Nannan, Wang Jinjun. Synthesis of Chlorin Aldehydes with Chlorophyllous Skeleton and Their Interactions with Protein [J]. Chin. J. Org. Chem., 2017, 37(7): 1814-1823.
[4]	Li Yanlong, Li Jiazhu, Zhang Shanguo, Wang Jinjun. Synthesis of (Methylenated)vinylated Chlorophyllous Chlorins and Study on Their Photosensitive Bactericidal Activities [J]. Chin. J. Org. Chem., 2016, 36(3): 562-571.
[5]	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.
[6]	Zhang Zhu, Jiang Qiyong, Zhang Qian, Wu Jin, Wang Jinjun. Structure Transformations on the Groups Linked with C-Pyrrol Subring of Pheophorbide-a and Synthesis of Chlorin Derivatives [J]. Chin. J. Org. Chem., 2015, 35(9): 1929-1938.
[7]	Gao Na, Zhang Shanguo, Wang Zhen, Wang Jinjun. Oxidation Reactions of Chlorophyll Degradation Products with Thallum Nitrate and Synthesis of Chlorophyllous Chlorins Derivatives [J]. Chin. J. Org. Chem., 2015, 35(8): 1715-1725.
[8]	Li Jinling, Xie Baozhan, Peng Jin. Synthesis of Bisanthene-Based Polycyclic Aromatic Hydrocarbons [J]. Chin. J. Org. Chem., 2015, 35(7): 1441-1450.
[9]	Liu Hongyao, Zhu Guohua, Liu Ranran, Jin Yingxue,Qi Caixia, Wang Jinjun. Chemical Modifications of Purpurin-18 and Synthesis of Chlorophyllous Chlorins Derivatives [J]. Chin. J. Org. Chem., 2015, 35(6): 1320-1329.
[10]	Zhang Shanguo, Li Jiazhu, Zhang Peng, Qi Caixia, Wang Jinjun. Transformation for Exocyclic Ring of Pheophorbide and Syn-thesis of Chlorophyllous Degradation Derivatives [J]. Chin. J. Org. Chem., 2015, 35(5): 1060-1068.
[11]	Yang Xiaoying, Zhang Shanguo, Zhang Peng, Zhang Qian, Wang Zhen, Jin Yingxue, Qi Caixia, Wang Jinjun. Chemical Reactions of 13²-Oxo-pyropheophorbide and Synthesis of Chlorophyllous Chlorins Derivatives [J]. Chin. J. Org. Chem., 2015, 35(1): 181-190.
[12]	Ji Jianye, Xia Shangwen, Liu Yang, Yin Jungang, Qi Caixia, Wang Jinjun. Synthesis of Chlorophyllous Chlorin Derivatives Possessing Stereo-isomeric Character [J]. Chin. J. Org. Chem., 2014, 34(6): 1138-1147.
[13]	Yang Xiaoying, Tan Guanghui, Qu Fengyu, Jin Yingxue, Wang Jinjun. Synthesis of Phenylhydrazone and Amino acid Schiff Base of Pyropheophorbide-a [J]. Chin. J. Org. Chem., 2014, 34(6): 1206-1211.
[14]	Xu Xisen, Yao Nannan, Liu Yang, Yin Jungang, Qi Caixia, Wang Jinjun. Reaction of meso-Pyropheophorbide-a and Synthesis of Chlorophyllous Chlorin Derivatives [J]. Chin. J. Org. Chem., 2014, 34(5): 938-947.
[15]	Liu Yang, Xu Xisen, Li Jiazhu, Yin Jungang, Qi Caixia, Wang Jinjun. Cyclopropylation of Chlorophyllous Degradation Products and Synthesis of Chlorin Derivatives [J]. Chin. J. Org. Chem., 2014, 34(3): 552-560.

C(3)-乙烯基的化学修饰与含氧基团取代的叶绿素-a衍生物的合成

Modification of C(3)-Vinyl Group and Synthesis of Oxygenic Group-Substituted Chorophyll-a Derivatives

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