Citation: LIU Yan-Zhu*, HUANG Yi-Ning, LI Xia, ZHANG Ling, LI Yong-Xiu*. Coordination-Mediated Radical Nitration of Methyl Salicylate by Copper(Ⅱ) Nitrate with High Regioselectivity[J]. Chinese Journal of Inorganic Chemistry, ;2014, 30(1): 121-126. doi: 10.11862/CJIC.2014.037 shu

Coordination-Mediated Radical Nitration of Methyl Salicylate by Copper(Ⅱ) Nitrate with High Regioselectivity

1.
Department of Chemistry, School of Science, Nanchang University, Jiangxi 330031, China

Received Date: 26 September 2013
Available Online: 4 November 2013
Fund Project:

High yield and para-selective products were obtained by the nitration of methyl salicylate (MeS) and copper(Ⅱ) nitrate(CuN). The results of electron absorption spectra (EAS),Cyclic Voltammetry(CV) and electrospray ionization mass spectra (ESIMS) reveal that the reaction favors a radical nitration mechanism. It is the coordination of MeS with CuNthat promotes the splitting of N-O bonds of nitrate group in CuN, and results in the formation of nitro radicals, oxygen radicals and complex radicals. The nitro radicals can react with MeS or the complexes of MeS to form nitration products. The nitrated complexes immediately turn to methyl nitrosalicylate by Cu(Ⅱ) ions being hydrolyzed to copper(Ⅱ) oxides.
- methyl salicylate;Cu(Ⅱ) nitrate;radical nitration;coordination,
1. [1]
  [1] Grenier J C, Catteau J P, Cotelle P. Synth. Commun., 1999, 29:1201-1208
2. [2]
  [2] Mellor J M, Mittoo S, Millar R W, et al. Tetrahedron Lett., 2000, 56:8019-8024
3. [3]
  [3] Tapia R, Tones G, Valdenama J A. Synth.Commun., 1986, 16:681-687
4. [4]
  [4] Riego J M, Sedin Z, Tortata C, et al. Tetrahedron Lett., 1996, 37:513-516
5. [5]
  [5] Chavez F, Suarez S, Diaz M A. Synth. Commun., 1994, 24: 2325-2339
6. [6]
  [6] Iranpoor N, Firouzbadi H, Nowrouzi N. Tetrahedron Lett., 2006, 47:6879-6881
7. [7]
  [7] Ashley B, Widyanti P, Sanjoto S V. Tetrahedron Lett., 2007, 48:3945-3947
8. [8]
  [8] Xin W, Mufaro A D, Albert J F. Tetrahedron Lett., 2006, 47: 7667-7669
9. [9]
  [9] Laszlo P. Acc. Chem. Res., 1986, 19:121-127
10. [10]
  [10] Campos P J, Garcia B, Rodriguez M A. Tetrahedron Lett., 2000, 41:979-982
11. [11]
  [11] Firouzabadi H, Iranpoor N, Zolfigol M A. Synth. Commun., 1997, 27:3301-3311
12. [12]
  [12] (a) Suzuki H, Yonezawa S, Nonoyama N T, et al. Chem. Soc. Perkin Trans. I. 1996:2385-2389
13. [13]
  (b) Bak R R, Smallridge A. J. Tetrahedron Lett., 2001, 42: 6767-6769
14. [14]
  (c) Rajagopal R, Srinivasan K V. Synth. Commun., 2003, 33:961-967
15. [15]
  [13] Iranpoor N, Firouzabadi H, Zolfigol M A. Synth. Commun., 1998, 28:2773-2781
16. [16]
  [14] Bose A K, Ganguly S N, Pombo V E, et al. Tetrahedron Lett., 2006, 47:1885-1888
17. [17]
  [15] Zolfigol M A, Ghaemi E, Madrakian E. Synth. Commun., 2000, 30:1689-1694
18. [18]
  [16] Wang P C, Lu M, Zhu J, et al. Catal. Commun., 2011, 14:42-45
19. [19]
  [17] Nowrouzi N, Zareh J M. Tetrahedron Lett., 2011, 52:5081-5084
20. [20]
  [18] Pervez H, Onyisiuka S O, Rooney J R, Sukling C J. Tetrahedron, 1988, 44:4555-4559
21. [21]
  [19] Queiroz J F, Carneiro J W, Sabino A A. J. Org. Chem., 2006, 71:6192-6203
22. [22]
  [20] LIU Yan-Zhu(刘艳珠), ZHANG Li(张玲), LI Yong-Xiu (李永绣), et al. Acta Phys.-Chim. Sin. (物理化学学报), 2009, 25:2118-2121
23. [23]
  [21] LI Xia(李霞), LIU Yan-Zhu(刘艳珠), LI Yong-Xiu(李永绣), et al. Fine Chemical Intermediates(精细化工中间体), 2009, 39:40-43
24. [24]
  [22] LIU Yan-Zhu(刘艳珠), LI Xia(李霞), LI Yong-Xiu(李永绣), et al. Appl. Chem. Indus. (应用化工), 2009, 38(11):1571-1574
25. [25]
  [23] YANG Bao-Shou(杨保收), CHEN Yue(陈越), DONG Mei (董梅), et al. Animal Science and Veterinary Medicine(动物科学和动物医学), 1999, 16:17-19
1. [1]
  Ping Song , Nan Zhang , Jie Wang , Rui Yan , Zhiqiang Wang , Yingxue Jin . Experimental Teaching Design on Synthesis and Antitumor Activity Study of Cu-Pyropheophorbide-a Methyl Ester. University Chemistry, 2024, 39(6): 278-286. doi: 10.3866/PKU.DXHX202310087
2. [2]
  Zijian Zhao , Yanxin Shi , Shicheng Li , Wenhong Ruan , Fang Zhu , Jijun Jiang . A New Exploration of the Preparation of Polyacrylic Acid by Free Radical Polymerization Based on the Concept of Green Chemistry. University Chemistry, 2024, 39(5): 315-324. doi: 10.3866/PKU.DXHX202311094
3. [3]
  Ming Li , Zhaoyin Li , Mengzhu Liu , Shaoxiang Luo . Unveiling the Artistry of Mordant Dyeing: The Coordination Chemistry Beneath. University Chemistry, 2024, 39(5): 258-265. doi: 10.3866/PKU.DXHX202311085
4. [4]
  Quanguo Zhai , Peng Zhang , Wenyu Yuan , Ying Wang , Shu'ni Li , Mancheng Hu , Shengli Gao . Reconstructing the “Fundamentals of Coordination Chemistry” in Inorganic Chemistry Course. University Chemistry, 2024, 39(11): 117-130. doi: 10.12461/PKU.DXHX202403065
5. [5]
  Jiapei Zou , Junyang Zhang , Xuming Wu , Cong Wei , Simin Fang , Yuxi Wang . A Comprehensive Experiment Based on Electrocatalytic Nitrate Reduction into Ammonia: Synthesis, Characterization, Performance Exploration, and Applicable Design of Copper-based Catalysts. University Chemistry, 2024, 39(6): 373-382. doi: 10.3866/PKU.DXHX202312081
6. [6]
  Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018
7. [7]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087
8. [8]
  Xuyang Wang , Jiapei Zhang , Lirui Zhao , Xiaowen Xu , Guizheng Zou , Bin Zhang . Theoretical Study on the Structure and Stability of Copper-Ammonia Coordination Ions. University Chemistry, 2024, 39(3): 384-389. doi: 10.3866/PKU.DXHX202309065
9. [9]
  Jiajia Li , Xiangyu Zhang , Zhihan Yuan , Zhengyang Qian , Jian Zhu . 3D Printing Based on Photo-Induced Reversible Addition-Fragmentation Chain Transfer Polymerization. University Chemistry, 2024, 39(5): 11-19. doi: 10.3866/PKU.DXHX202309073
10. [10]
  Qin Hou , Jiayi Hou , Aiju Shi , Xingliang Xu , Yuanhong Zhang , Yijing Li , Juying Hou , Yanfang Wang . Preparation of Cuprous Iodide Coordination Polymer and Fluorescent Detection of Nitrite: A Comprehensive Chemical Design Experiment. University Chemistry, 2024, 39(8): 221-229. doi: 10.3866/PKU.DXHX202312056
11. [11]
  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
12. [12]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-. doi: 10.3866/PKU.WHXB202406029
13. [13]
  Yanan Liu , Yufei He , Dianqing Li . Preparation of Highly Dispersed LDHs-based Catalysts and Testing of Nitro Compound Reduction Performance: A Comprehensive Chemical Experiment for Research Transformation. University Chemistry, 2024, 39(8): 306-313. doi: 10.3866/PKU.DXHX202401081
14. [14]
  Guang Huang , Lei Li , Dingyi Zhang , Xingze Wang , Yugai Huang , Wenhui Liang , Zhifen Guo , Wenmei Jiao . Cobalt’s Valor, Nickel’s Foe: A Comprehensive Chemical Experiment Utilizing a Cobalt-based Imidazolate Framework for Nickel Ion Removal. University Chemistry, 2024, 39(8): 174-183. doi: 10.3866/PKU.DXHX202311051
15. [15]
  Lirui Shen , Kun Liu , Ying Yang , Dongwan Li , Wengui Chang . Synthesis and Application of Decanedioic Acid-N-Hydroxysuccinimide Ester: Exploration of Teaching Reform in Comprehensive Applied Chemistry Experiment. University Chemistry, 2024, 39(8): 212-220. doi: 10.3866/PKU.DXHX202312035
16. [16]
  Jinghua Wang , Yanxin Yu , Yanbiao Ren , Yesheng Wang . Integration of Science and Education: Investigation of Tributyl Citrate Synthesis under the Promotion of Hydrate Molten Salts for Research and Innovation Training. University Chemistry, 2024, 39(11): 232-240. doi: 10.3866/PKU.DXHX202402057
17. [17]
  Gonglan Ye , Xia Yin , Feng Xu , Peng Yang , Yingpeng Wu , Huilong Fei . Innovations in “Four-in-One” Inorganic Chemistry Education. University Chemistry, 2024, 39(8): 136-141. doi: 10.3866/PKU.DXHX202401071
18. [18]
  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
19. [19]
  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
20. [20]
  Li Zhou , Dongyan Tang , Yunchen Du . Focusing on the Cultivation of Outstanding Talents: A “Five in One” Approach to Promoting the Construction of Chemical Experimental and Practical Teaching System. University Chemistry, 2024, 39(7): 121-128. doi: 10.12461/PKU.DXHX202405037

Get Citation

PDF

XML

Metrics

PDF Downloads(457)
Abstract views(1023)
HTML views(125)

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