Citation: Gao Na, Wang Zhen, Wu Jin, Liu Chao, Wang Jinjun. Synthesis of Cyanided Chlorophyllous Chlorin Derivatives and Study on Their Photodynamic Activities[J]. Chinese Journal of Organic Chemistry, ;2016, 36(3): 580-589. doi: 10.6023/cjoc201506037 shu

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

Corresponding author: Wang Jinjun, wjj1955@163.com
Received Date: 30 June 2015
Revised Date: 16 November 2015

Fund Project: the National Natural Science Foundations of China 21272048

Figures(4)

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 and¹H 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.
- chlorophyll-a,
- chlorin,
- chemical modification,
- cyanation reaction,
- photodynamic activity
1. [1]
  Liu, C.; Dobhal, M. P.; Ethirajan, M.; Missert, J. R.; Pandey, R. K.; Balasubramanian, S.; Sukumaran, D. K.; Zhang, M.; Kadish, K. M.; Ohkubo, K.; Fukuzumi, S. J. Am. Chem. Soc, 2008, 130, 14311.
  (b) Machida, S.; Isoda, Y.; Kunieda, M.; Tamiaki, H. Tetrahedron Lett. 2012, 53, 6277.
  (c) Fajer, J. Photosynth. Res. 2004, 80, 165.
  (d) Bruckner, C.; McCarthy, J. R.; Daniell, H. W.; Pendon, Z. D.; Iiagan, R. P.; Francis, T. M.; Ren, L.; Birge, R. R.; Frank, H. A. Chem. Phys. 2003, 294, 285.
2. [2]
  Chen, Y. H.; Li, G. L.; Pandey, R. K. Curr. Org. Chem. 2004, 8, 1105.
  (b) Wang, J.-J. Chin. J. Org. Chem. 2005, 25, 1353 (in Chinese).
  (王进军, 有机化学, 2005, 25, 1353.) (c) Gil, M.; Bieniaszl, M.; Seshadri, M.; Fisher, D.; Ciesielski, M. J.; Chen, Y.; Pandey, R. K.; Kozbor, D. Brit. J. Cancer 2011, 103(10), 1.
  (d) Ethirajan, M.; Joshi, P.; William, W. H.; Ohkubo, K.; Fukuzumi, S.; Pandey, R. K. Org. Lett, 2011, 8, 1956.
  (e) Bellnier, D. A.; Greco, W. R.; Loewen, G. M.; Nava, H.; Oseroff, A. R.; Pandey, R. K.; Tsuchida, T.; Dougherty, T. J. Cancer Res. 2003, 63, 1806;
3. [3]
  Ethirajan, M.; Joshi, P.; William, W. H.; Ohkubo, K.; Fukuzumi, S.; Pandey, R. K. Org. Lett. 2011, 13, 1956.
  (b) Pavlov, V. Y.; Ponomarev, G. V. Chem. Heterocycl. Compd. 2004, 40, 393.
  (c) Li, J.-Z.; Zhang, P.; Zhang, S.-G.; Yin, J.-G.; Wang, J.-J. Org. Biol. Chem. 2015, 13, 1992.
4. [4]
  Pandey, S. K.; Zheng, X.; Morgan, J.; Missert, J. R.; Liu, T.-H.; Shibata, M.; Bellnier, D. A.; Oseroff, A. R.; Henderson, B. W.; Dougherty, T. J.; Pandey, R. K. Mol. Pharm. 2007, 4, 448.
  (b) Kozyrey, A. N.; Chen, Y.-H.; Goswami, L. N.; Tabaczynaki, W. A.; Pandey, R. K. J. Org. Chem. 2006, 71, 1949.
  (c) Li, J.-Z.; Zhang, P.; Yao, N.-N.; Zhao, L.-L.; Wang, J, -J.; Shim, Y.-K. Tetrahedron Lett. 2014, 55, 1086
5. [5]
  Xu, X.-S.; Yao, N.-N.; Liu, Y.; Yin, J.-G.; Qi, C.-X.; Wang, J.-J. Chin. J. Org. Chem. 2014, 34, 938 (in Chinese).
  (徐希森, 姚楠楠, 刘洋, 殷军港, 祁彩霞, 王进军, 有机化学, 2014, 34, 938.)
  (b) Liu, Y.; Xu, X.-S.; Li, J.-Z.; Yin, J.-G.; Qi, C.-X.; Wang, J.-J. Chin. J. Org. Chem. 2014, 34, 552 (in Chinese).
  (刘洋, 徐希森, 李家柱, 殷军港, 祁彩霞, 王进军, 有机化学, 2014, 34, 552.)
  (c) Sasaki, S.; Mizutani, K.; Kunieda, M.; Tamiaki, H. Tetrahedron 2011, 67, 6065.
6. [6]
  Wang, J.-J.; Wang, P.; Li, J.-Z.; Jakus, J.; Shin, Y.-K. Bull. Korean Chem. Soc. 2011, 32, 3473.
  (b) Wang, J.-J.; Yin, Y.-F.; Yang, Z. J. Iran. Chem. Soc. 2013, 10, 583.
  (c) Wang, J.-J.; Ji, J.-Y.; Han, G. F.; Wu, X.-R.; Wang, L.-M.; Shin, Y.-K. Acta Chim. Sinica 2004, 62, 302 (in Chinese).
  (王进军, 纪建业, 韩光范, 邬旭然, 王鲁敏, 沈荣基, 化学学报, 2004, 62, 302.) (d) Luca, A. R.; Giacomelli, G.; Porcheddu, A. J. Org. Chem. 2002, 67, 6272.
7. [7]
  Ji, J.-Y.; Wang, L. M.; Jing, J.-R.; Han, G.-F.; Wang, J. J. Chin. J. Org. Chem. 2007, 27, 493 (in Chinese).
  (纪建业, 王鲁民, 荆济荣, 韩光范, 王进军, 有机化学, 2007, 27, 493.)
  (b) Wang, J.-J.; Li, J.-Z.; Li, Y.-W.; Jakus, J.; Shim, Y.-K. J. Porphyrins Phthalocyanines 2010, 14, 859.
  (c) Wang, J.-J.; Li, J.-Z.; Jakus. J.; Shim, Y. K. J. Porphyrins Phthalocyanines 2012, 16, 122.
  (d) Anilkumar, R.; Chandrsekhar, S. Tetrahedron Lett. 2001, 42, 5427.
8. [8]
  Zhang, Q. M.S. Thesis, Yantai University, Yantai, 2011 (in Chinese).
  (张千, 硕士论文, 烟台大学, 烟台, 2011.)
9. [9]
  Liu, Y. M.S. Thesis, Yantai University, Yantai, 2014 (in Chinese).
  (刘洋, 硕士论文, 烟台大学, 烟台, 2014.)
10. [10]
  Arisawa, M.; Yanaguchi, M. Org. Lett. 2001, 3, 311.
  (b) Kikugawa, Y.; Tsuji, C.; Miyazawa, E.; Sakamoto, T. Tetrahedron Lett. 2001, 42, 2337.
11. [11]
  Ji, J.-Y.; Yin, J.-G.; Zhang, Q.; Liu, C.; Qi, C.-X.; Wang, J. J. Chin. J. Org. Chem. 2014, 34, 2047 (in Chinese).
  (纪建业, 殷军港, 张千, 刘超, 祁彩霞, 王进军, 有机化学, 2014, 34, 2047.)
  (b) Wang, L.-M.; Wang, P.; Liu, C.; Jin, Y.-X.; Wang, J.-J. Chin. J. Org. Chem. 2012, 32, 1700 (in Chinese).
  (王鲁敏, 王朋, 刘超, 金英学, 王进军, 有机化学, 2012, 32, 1700.)
12. [12]
  Smith, K. M.; Gogg, D. A.; Simpson, D. J. J. Am. Chem. Soc. 1985, 107, 4946. doi: 10.1021/ja00303a021
1. [1]
  Jinyao Du , Xingchao Zang , Ningning Xu , Yongjun Liu , Weisi Guo . Electrochemical Thiocyanation of 4-Bromoethylbenzene. University Chemistry, 2024, 39(6): 312-317. doi: 10.3866/PKU.DXHX202310039
2. [2]
  Qin Li , Kexin Yang , Qinglin Yang , Xiangjin Zhu , Xiaole Han , Tao Huang . Illuminating Chlorophyll: Innovative Chemistry Popularization Experiment. University Chemistry, 2024, 39(9): 359-368. doi: 10.3866/PKU.DXHX202309059
3. [3]
  Zihan Lin , Wanzhen Lin , Fa-Jie Chen . Electrochemical Modifications of Native Peptides. University Chemistry, 2025, 40(3): 318-327. doi: 10.12461/PKU.DXHX202406089
4. [4]
  Yikai Wang , Xiaolin Jiang , Haoming Song , Nan Wei , Yifan Wang , Xinjun Xu , Cuihong Li , Hao Lu , Yahui Liu , Zhishan Bo . 氰基修饰的苝二酰亚胺衍生物作为膜厚不敏感型阴极界面材料用于高效有机太阳能电池. Acta Physico-Chimica Sinica, 2025, 41(3): 2406007-. doi: 10.3866/PKU.WHXB202406007
5. [5]
  Chengqian Mao , Yanghan Chen , Haotong Bai , Junru Huang , Junpeng Zhuang . Photodimerization of Styrylpyridinium Salt and Its Application in Silk Screen Printing. University Chemistry, 2024, 39(5): 354-362. doi: 10.3866/PKU.DXHX202312014
6. [6]
  Yinuo Wang , Siran Wang , Yilong Zhao , Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063
7. [7]
  Xin Lv , Hongxing Zhang , Kaibo Duan , Wenhui Dai , Zhihui Wen , Wei Guo , Junsheng Hao . Lighting the Way Against Cancer: Photodynamic Therapy. University Chemistry, 2024, 39(5): 70-79. doi: 10.3866/PKU.DXHX202309090
8. [8]
  Linjie ZHU , Xufeng LIU . Synthesis, characterization and electrocatalytic hydrogen evolution of two di-iron complexes containing a phosphine ligand with a pendant amine. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 939-947. doi: 10.11862/CJIC.20240416
9. [9]
  Jiageng Li , Putrama . 数值积分耦合非线性最小二乘法一步确定反应动力学参数. University Chemistry, 2025, 40(6): 364-370. doi: 10.12461/PKU.DXHX202407098
10. [10]
  Lijuan Wang , Yuping Ning , Jian Li , Sha Luo , Xiongfei Luo , Ruiwen Wang . Enhancing the Advanced Nature of Natural Product Chemistry Laboratory Courses with New Research Findings: A Case Study of the Application of Berberine Hydrochloride in Photodynamic Antimicrobial Films. University Chemistry, 2024, 39(11): 241-250. doi: 10.12461/PKU.DXHX202403017
11. [11]
  Shiyang He , Dandan Chu , Zhixin Pang , Yuhang Du , Jiayi Wang , Yuhong Chen , Yumeng Su , Jianhua Qin , Xiangrong Pan , Zhan Zhou , Jingguo Li , Lufang Ma , Chaoliang Tan . 铂单原子功能化的二维Al-TCPP金属-有机框架纳米片用于增强光动力抗菌治疗. Acta Physico-Chimica Sinica, 2025, 41(5): 100046-. doi: 10.1016/j.actphy.2025.100046
12. [12]
  Yeyun Zhang , Ling Fan , Yanmei Wang , Zhenfeng Shang . Development and Application of Kinetic Reaction Flasks in Physical Chemistry Experimental Teaching. University Chemistry, 2024, 39(4): 100-106. doi: 10.3866/PKU.DXHX202308044
13. [13]
  Zhongyan Cao , Youzhi Xu , Menghua Li , Xiao Xiao , Xianqiang Kong , Deyun Qian . Electrochemically Driven Denitrative Borylation and Fluorosulfonylation of Nitroarenes. University Chemistry, 2025, 40(4): 277-281. doi: 10.12461/PKU.DXHX202407017
14. [14]
  Dan Liu . 可见光-有机小分子协同催化的不对称自由基反应研究进展. University Chemistry, 2025, 40(6): 118-128. doi: 10.12461/PKU.DXHX202408101
15. [15]
  Shengbiao Zheng , Liang Li , Nini Zhang , Ruimin Bao , Ruizhang Hu , Jing Tang . Metal-Organic Framework-Derived Materials Modified Electrode for Electrochemical Sensing of Tert-Butylhydroquinone: A Recommended Comprehensive Chemistry Experiment for Translating Research Results. University Chemistry, 2024, 39(7): 345-353. doi: 10.3866/PKU.DXHX202310096
16. [16]
  Dexin Tan , Limin Liang , Baoyi Lv , Huiwen Guan , Haicheng Chen , Yanli Wang . Exploring Reverse Teaching Practices in Physical Chemistry Experiment Courses: A Case Study on Chemical Reaction Kinetics. University Chemistry, 2024, 39(11): 79-86. doi: 10.12461/PKU.DXHX202403048
17. [17]
  Yiying Yang , Dongju Zhang . Elucidating the Concepts of Thermodynamic Control and Kinetic Control in Chemical Reactions through Theoretical Chemistry Calculations: A Computational Chemistry Experiment on the Diels-Alder Reaction. University Chemistry, 2024, 39(3): 327-335. doi: 10.3866/PKU.DXHX202309074
18. [18]
  Xiaoyang Li , Xiaowei Huang , Yimeng Zhang , Huan Liu , Shao Jin , Junpeng Zhuang . Comprehensive Chemical Experiments on the Synthesis of 1,3-Dibromo-5,5-Dimethylhydantoin and Its Application as a Brominating Reagent. University Chemistry, 2025, 40(7): 286-293. doi: 10.12461/PKU.DXHX202408035
19. [19]
  Xuzhen Wang , Xinkui Wang , Dongxu Tian , Wei Liu . Enhancing the Comprehensive Quality and Innovation Abilities of Graduate Students through a “Student-Centered, Dual Integration and Dual Drive” Teaching Model: A Case Study in the Course of Chemical Reaction Kinetics. University Chemistry, 2024, 39(6): 160-165. doi: 10.3866/PKU.DXHX202401074
20. [20]
  Jiayu Gu , Siqi Wang , Jun Ling . Kinetics of Living Copolymerization: A Brief Discussion. University Chemistry, 2025, 40(4): 100-107. doi: 10.12461/PKU.DXHX202406012

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(1004)
HTML views(138)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142