Citation: Zhang Zhu, Li Jiazhu, Wang Xinyue, Ma Jihua, Wang Xu, Wang Jinjun. Nitration (Nitroalkylation) of Pheophorbide and Synthesis of Chlorophyllous Chlorin Derivatives[J]. Chinese Journal of Organic Chemistry, ;2020, 40(9): 2895-2903. doi: 10.6023/cjoc202004054 shu

Nitration (Nitroalkylation) of Pheophorbide and Synthesis of Chlorophyllous Chlorin Derivatives

Zhang Zhu ¹ ,
Li Jiazhu ² ,
Wang Xinyue ² ,
Ma Jihua ² ,
Wang Xu ² ,
Wang Jinjun ^1,2,,

a.
Department of Food & Biological Engineering, Wenjing College, Yantai University, Yantai, Shandong 264005
b.
College of chemistry and chemical engineering, Yantai University, Yantai, Shandong 264005

Corresponding author: Wang Jinjun, wjj1955@163.com
Received Date: 30 April 2020
Revised Date: 31 May 2020
Available Online: 11 June 2020
Fund Project: the National Natural Science Foundations of China 21272048Project supported by the National Natural Science Foundations of China (No. 21272048) and the Natural Science Foundation of Shandong Province (No. ZR2015BQ012)the Natural Science Foundation of Shandong Province ZR2015BQ012

Figures(6)

Pyropheophorbide-a methyl ester was used as a starting material, and the chemical modification was carried out making use of its active groups attached to the chlorin periphery to establish the formyl group, ketene and α-diketone moieties around the N²¹-N²³ axis. The nitrations or nitroalkylations at 3-, 12-, 20-position and on the exocyclic ring were performed by the electrophilic substitution on the aromatic macrocyclic chromophore, Henry reaction at the active carbonyl groups, and Michael addition to the β-keto ester and the ketene structures on the exocyclic ring as different donor-acceptor. A series of unreported nitro(nitroalkyl) substituted chlorins related to chlorophyll were synthesized and their chemical structures were characterized by elemental analysis, UV-Vis, IR and ¹H NMR spectra.
- chlorophyll,
- pheophorbide,
- chlorin,
- nitration(nitroalkylation) reaction,
- synthesis
1. [1]
  (a) Ali, H.; Vanlier, J. E. In Handbook of Porphyrin Science, Vol. 4, Eds.: Kadish, K. M.; Smith, K. M.; Guilard, R., World Scientific Publishing Company, Singapore, 2010, p. 1.
  (b) Ethirajan, M.; Patel, N. J.; Pandey, R. K. In Handbook of Porphyrin Science, Vol. 4, Eds.: Kadish, K. M.; Smith, K. M.; Guilard, R., World Scientific Publishing Company, Singapore, 2010, p. 249.
  (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.
2. [2]
  (a) 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) Li, J.; He, N.; Liu, Y.; Zhang, Z.; Zhang, X.; Han, X.; Gai, Y.; Liu, Y.; Yin, J.; Wang, J. Dyes Pigm. 2017, 146, 189.
  (c) Jiang, Q.-Y.; Zhang, Z.; Liu, Y.; Yao, N.-N.; Wang, J.-J. Chin. J. Org. Chem. 2017, 37, 1814(in Chinese). (姜齐永, 张珠, 刘洋, 姚楠楠, 王进军, 有机化学, 2017, 37, 1814.)
3. [3]
  (a) Wang, J.-J. Chin. J. Org. Chem. 2005, 25, 1353(in Chinese). (王进军, 有机化学, 2005, 25, 1353.)
  (b) Ethirajan, M.; Joshi, P.; William, W. H.; Ohkubo, K.; Fukuzumi, S.; Pandey, R. K. Org. Lett. 2011, 8, 1956.
  (c) 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.
4. [4]
  (a) Ethirajan, M.; Chen, P.; Ohulchanskyy, T. Y.; Goswami, L. N.; Gupta, A.; Srivatsan, A.; Dobhal, M. P.; Missert, J. R.; Prasad, P. N.; Kadish, K. M. Chem. Eur. J. 2013, 19, 6670.
  (b) Pandey, R. K.; Goswami, L. N.; Chen, Y.; Gryshuk, A.; Missert, J. R.; Oseroff, A.; Dougherty, T. J. Lasers Surg. Med. 2006, 467, 445.
  (c) Tamiaki, H.; Wada, A.; Matsubara, S. J. Photochem. Photobiol. A. Chem. 2018, 353, 581.
5. [5]
  (a) 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) Duan, S.; Dall'Agnese, C.; Chen, G.; Wang, X.-F.; Tamiaki, H.; Yamamoto, Y.; Ikeuchi, T.; Sasaki, S. ACS Energy Lett. 2018, 3, 1708.
6. [6]
  (a) Wang, L.-M.; Wang, Z.; Yang, Z.; Jin, Y.-X.; Wang, J.-J. Chin. J. Org. Chem. 2012, 32, 2154(in Chinese). (王鲁敏, 王振, 杨泽, 金英学, 王进军, 有机化学, 2012, 32, 2154.)
  (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) Gao, N.; Li, J.-Z.; Li, Y.-L.; Wang, Z.; Wang, J.-J. Chin. Chem. Lett. 2016, 27, 789.
  (d) Wu, H.-Q.; Wang, X.-M.; Liu, Y.; Zhao, Y.; Shim, Y.-K.; Yoon, I.; Xu, X.-M.; Li, J.-Z. Bull. Korean Chem. Soc. 2020, 41, 504.
7. [7]
  (a) Wang, J.-J.; Wang, P.; Li, J.-Z.; Jakus, J.; Shin, Y.-K. Bull. Korean Chem. Soc. 2011, 32, 3473.
  (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.)
  (c) 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.)
  (d) Shoji, S.; Nomura, Y.; Tamiaki, H. Tetrahedron 2020, 76, 131130.
8. [8]
  (a) Li, J.-Z.; Zhang, P.; Yao, N.-N.; Zhao, L.-L.; Wang, J.-J.; Shim, Y.-K. Tetrahedron Lett. 2014, 55, 1086.
  (b) Liu, Y.; Wu, H.; Zhang, X.; Pan, Q.; Wang, X.-M.; Peng, W.; Yin, J.-G.; Li, G.-Z.; Li, J.-Z.; Wang, J.-J. Chem. Pap. 2018, 72, 1389.
  (c) Wang, J.-J.; Li, J.-Z.; Jakus. J.; Shim, Y. K. J. Porphyrins Phthalocyanines 2012, 16, 122.
  (d) Takahashi, T.; Ogasawara, S.; Shinozaki, Y.; Tamiaki, H. Bull. Chem. Soc. Jpn. 2020, 93, 467.
  (e) Zhang, Z.; Xu, X.; Li, Y.; Li, J.; Wang, J. Chin. J. Org. Chem. 2018, 38, 2993(in Chinese). (张珠, 徐希森, 李彦龙, 李家柱, 王进军, 有机化学, 2018, 38, 2993.)
9. [9]
  (a) Silva, A. M. G.; Tomé, A. C.; Neves, M. G. P. M. S.; Cavaleiro, J. A. S. Synlett 2002, 1155.
  (b) Richeter, S. B.; Jeandon, C.; Gisselbrecht, J.-P.; Graff, R.; Ruppert, R.; Callot, H. J. Inorg. Chem. 2004, 43, 251.
10. [10]
  (a) Richeter, S.; Hadj-aissa, A.; Taffin, C.; van der Lee, A.; Leclercq, D. Chem. Commun. 2007, 2148.
  (b) Mandoj, F.; Nardis, S.; Pudi, R.; Lvova, L.; Fronczek, F. R.; Smith, K. M.; Prodi, L.; Genovese, D.; Paolesse, R. Dyes Pigm. 2013, 99, 136.
11. [11]
  (a) 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) Wang, Z.; Yang, Z.; Liu, Y.; Xu, X.-S.; Qi, C.-X.; Wang, J.-J. Chin. J. Org. Chem. 2012, 32, 2300(in Chinese). (王振, 杨泽, 刘洋, 徐希森, 祁彩霞, 王进军, 有机化学, 2012, 32, 2300.)
  (c) Tamiaki, H.; Ohata, M.; Kinoshita, Y.; Machida, S. Tetrahedron 2014, 70, 1629.
12. [12]
  Smith, K. M.; Gogg, D. A.; Simpson, D. J. J. Am. Chem. Soc. 1985, 107, 4946. doi: 10.1021/ja00303a021
13. [13]
  (a) Doyle, A. G.; Jacobsen, E. N. J. Am. Chem. Soc. 2007, 107, 5713.
  (b) Shi. M.; Chen, L.-H.; Li, C.-J. Chem. Rev, 2005, 127, 3790.
  (c) Inokuma, T.; Hoashi, Y.; Takemoto, Y. J. Am. Chem. Soc, 2006, 128, 9413.
  (d) Jung, C. K.; KrisChe, M. J. J. Am. Chem. Soc, 2006, 128, 17051.
14. [14]
  (a) Li, J.-Z.; Cui, B.-C.; Wang, J.-J.; Shim, Y.-K. Bull. Korean Chem. Soc. 2011, 32, 2465.
  (b) Zhang, S.-G. M.S. Thesis, Yantai University, Yantai, 2015 (in Chinese). (张善国, 硕士论文, 烟台大学, 烟台, 2015.)
15. [15]
  Kureishi, Y.; Tamiaki, H. J. Porphyrins Phthalocyanines 1998, 2, 159. doi: 10.1002/(SICI)1099-1409(199803/04)2:2<159::AID-JPP62>3.0.CO;2-Q
16. [16]
  Han, G.-F.; Wang, J.-J.; Qu, Y.; Shim, Y.-K. Chin. J. Org. Chem. 2006, 26, 43.
1. [1]
  Lifang HE , Yaoze LUO , Qiying SHI , Jianxin TANG , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and properties of hydrated tricyclohexyltin theophylline-7-acetic acid complex. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 632-640. doi: 10.11862/CJIC.20250244
2. [2]
  Liping GUO . Synthesis and crystal structure characterization of yttrium imido complex: The reactivity of 2-substituted-1-amino-o-carborane with yttrium dialkyl complex. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1409-1415. doi: 10.11862/CJIC.20250065
3. [3]
  Ran ZHUANG , Xinru WANG , Ruwei SHEN , Dunru ZHU . Syntheses, crystal structures and Hirshfeld surface analyses of three 3-pyridazinyl-substituted triaryltriazoles and their Cu(Ⅱ) complexes. Chinese Journal of Inorganic Chemistry, 2026, 42(8): 1712-1722. doi: 10.11862/CJIC.20260136
4. [4]
  Xinting XIONG , Zhiqiang XIONG , Panlei XIAO , Xuliang NIE , Xiuying SONG , Xiuguang YI . Synthesis, crystal structures, Hirshfeld surface analysis, and antifungal activity of two complexes Na(Ⅰ)/Cd(Ⅱ) assembled by 5-bromo-2-hydroxybenzoic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1661-1670. doi: 10.11862/CJIC.20240145
5. [5]
  Jing WU , Puzhen HUI , Huilin ZHENG , Pingchuan YUAN , Chunfei WANG , Hui WANG , Xiaoxia GU . Synthesis, crystal structures, and antitumor activities of transition metal complexes incorporating a naphthol-aldehyde Schiff base ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2422-2428. doi: 10.11862/CJIC.20240278
6. [6]
  Bin SUN , Heyan JIANG . Glucose-modified bis-Schiff bases: Synthesis and bio-activities in Alzheimer′s disease therapy. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1338-1350. doi: 10.11862/CJIC.20240428
7. [7]
  Lifang HE , Wenjie TANG , Yaoze LUO , Mingsheng LIANG , Jianxin TANG , Yuxuan WU , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two dialkyltin complexes constructed based on 2, 2′-bipyridin-6, 6′-dicarboxylic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1601-1609. doi: 10.11862/CJIC.20250012
8. [8]
  Lixing ZHANG , Yaowen WANG , Xu HAN , Junhong ZHOU , Jinghui WANG , Liping LI , Guangshe LI . Research progress in the synthesis of fluorine-containing perovskites and their derivatives. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1689-1701. doi: 10.11862/CJIC.20250007
9. [9]
  Qing ZHANG , Kexin ZHOU , Yanjun GUO , Guangjun CHEN , Bai HE , Bo YU , Songshan JIANG , Guoyuan YUAN , Huidong QIU . Preparation, functional modification, and applications of Fe₃O₄ nanoparticles. Chinese Journal of Inorganic Chemistry, 2026, 42(7): 1383-1411. doi: 10.11862/CJIC.20250344
10. [10]
  Kebo Xie , Qian Zhang , Fei Ye , Jungui Dai . A multi-enzymatic cascade reaction for the synthesis of bioactive C-oligosaccharides. Chinese Chemical Letters, 2024, 35(6): 109028-. doi: 10.1016/j.cclet.2023.109028
11. [11]
  Liming Li , Yanchang Liu , Peng Kang , Donghui Feng , Yuguang Zhang , Hangxing Ren , Jianrong Zeng , He Zhu , Qiang Li , Xiaoya Cui . Scalable and rapid liquid synthesis of PtNi electrocatalyst for hydrogen evolution reaction. Chinese Chemical Letters, 2026, 37(2): 112022-. doi: 10.1016/j.cclet.2025.112022
12. [12]
  Xiaoxia WANG , Ya'nan GUO , Feng SU , Chun HAN , Long SUN . Synthesis, structure, and electrocatalytic oxygen reduction reaction properties of metal antimony-based chalcogenide clusters. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1201-1208. doi: 10.11862/CJIC.20230478
13. [13]
  Genxiang Wang , Linfeng Fan , Peng Wang , Junfeng Wang , Fen Qiao , Zhenhai Wen . Efficient synthesis of nano high-entropy compounds for advanced oxygen evolution reaction. Chinese Chemical Letters, 2025, 36(4): 110498-. doi: 10.1016/j.cclet.2024.110498
14. [14]
  Nana Yang , Rui Yuan , Xinyue Fu , Xiao Tian , Jin Yu , Shengzhou Ma , Liuqing Wen , Jiabin Zhang . Concise synthesis of NDP-activated uronic acid by an oxidation reaction insertion strategy. Chinese Chemical Letters, 2025, 36(8): 110757-. doi: 10.1016/j.cclet.2024.110757
15. [15]
  Xia-Lin Dai , Yu-Hang Yao , Jian-Feng Zhen , Wei Gao , Jia-Mei Chen , Tong-Bu Lu . Reaction crystallization method based on deep eutectic solvents: A novel, green and efficient cocrystal synthesis approach. Chinese Chemical Letters, 2025, 36(11): 110413-. doi: 10.1016/j.cclet.2024.110413
16. [16]
  Lingchang Kong , Xiaoya Cui , Yujing Li , Kaiwen Yang , Hengxing Peng , Libing Liao , Guocheng Lv . Ultrafast synthesis of vacancy-rich IrO₂/TiO₂ for acidic oxygen evolution reaction. Chinese Chemical Letters, 2026, 37(7): 112375-. doi: 10.1016/j.cclet.2026.112375
17. [17]
  Tingting Liu , Ruting Lin , Yuyu Liu , Chen Chen , Qiufeng Huang , Yuzhi Sun , Shengyun Huang , Ibrahim Saana Amiinu , Zonghua Pu . Ultrafast carbothermal shock synthesis of transition metal phosphides in air for highly efficient hydrogen evolution reaction. Chinese Chemical Letters, 2026, 37(8): 111312-. doi: 10.1016/j.cclet.2025.111312
18. [18]
  Rong-Nan Yi , Wei-Min He . Photocatalytic Minisci-type multicomponent reaction for the synthesis of 1-(halo)alkyl-3-heteroaryl bicyclo[1.1.1]pentanes. Chinese Chemical Letters, 2024, 35(10): 110115-. doi: 10.1016/j.cclet.2024.110115
19. [19]
  Xiuhua Wang , Jianrong Steve Zhou . A dicationic nickel complex-catalyzed asymmetric synthesis of chiral benzylic amines: Evolution from reductive amination to borrowing hydrogen reaction. Chinese Chemical Letters, 2026, 37(2): 111148-. doi: 10.1016/j.cclet.2025.111148
20. [20]
  Zhuojun Duan , Peiyue Jin , Houying Xing , Jian Chen , Yueting Yang , Yawen Tan , Song Liu . Salt-assisted synthesis of WTe₂ contact electrodes for efficient MoS₂-based hydrogen evolution reaction. Chinese Chemical Letters, 2026, 37(2): 111917-. doi: 10.1016/j.cclet.2025.111917

Get Citation

PDF

XML

Metrics

PDF Downloads(4)
Abstract views(1577)
HTML views(200)

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