Citation: Chen Jingjing, Wang Yingshu, Yu Jun, Cheng Jiajia, Zheng Huidong. A Green and Scalable Cobalt(Ⅱ)-Catalyzed Oxidation of 2-Ethyl-3-methylpyrazine[J]. Chinese Journal of Organic Chemistry, ;2020, 40(1): 78-83. doi: 10.6023/cjoc201908001 shu

A Green and Scalable Cobalt(Ⅱ)-Catalyzed Oxidation of 2-Ethyl-3-methylpyrazine

a.
College of Materials Science and Engineering, Fuzhou University, Fuzhou 350108
b.
College of Chemical Engineering, Fuzhou University, Fuzhou 350108
c.
College of Chemistry, Fuzhou University, Fuzhou 350108

Corresponding author: Wang Yingshu, 1187562077@qq.com
Received Date: 1 August 2019
Revised Date: 2 September 2019
Available Online: 18 January 2019
Fund Project: the National Natural Science Foundation of China 21476049the University-Industry Cooperation Project of Fujian Province 2019H6010the Industrial Technology Joint Innovation Special Project of Fujian Province FG-2016005Project supported by the National Natural Science Foundation of China (No. 21476049), the Regional Development Project of Fujian Province (No. 2016H4023), the University-Industry Cooperation Project of Fujian Province (No. 2019H6010), the Industrial Technology Joint Innovation Special Project of Fujian Province (No. FG-2016005) and the Program for New Century Excellent Talents in University of Fujian Province (No. HG2017-17)the Regional Development Project of Fujian Province 2016H4023the Program for New Century Excellent Talents in University of Fujian Province HG2017-17

Figures(5)

A green and scalable oxidation of 2-ethyl-3-methylpyrazine (EMP) by tert-butylhydroperoxide was investigated with a catalytic system of cobalt(Ⅱ) and N-containing ligand. The effects of catalyst, ligand, solvent and temperature were compared, and the catalysis system of cobalt(Ⅱ) acetylacetonate and 2, 2-bipyridine gave the highest selectivity. Mechanistic study of this catalysis system suggested that the oxidation of EMP followed a free radical oxidation pathway, and a homogeneous reaction kinetics model was established to calculate the reaction rate constant and activation energy. The scale-up of the oxidation system was performed to check the scalability of the oxidation reaction, and the temperature control of the system was the key part of the process.
- 2-ethyl-3-methylpyrazine (EMP),
- 2-acetyl-3-methylpyrazine (AMP),
- allylic oxidation,
- reaction mechanism,
- kinetics,
- scale-up
1. [1]
  Mookherjee, B. D.; Klaiber, E. M. J. Org. Chem. 1972, 37, 511. doi: 10.1021/jo00968a047
2. [2]
  Cooper, J. C.; Luo, C.; Kameyama, R.; Humbeck, J. F. van J. Am. Chem. Soc. 2018, 140, 1243. doi: 10.1021/jacs.7b12864
3. [3]
  Moghaddam, F. M.; Mirjafary, Z.; Saeidian, H.; Javan, M. J. Synlett 2008, 892.
4. [4]
  Sterckx, H.; De Houwer, J.; Mensch, C.; Caretti, I.; Tehrani, K. A.; Herrebout, W. A.; Van Doorslaer, S.; Maes, B. U. W. Chem. Sci. 2016, 7, 346. doi: 10.1039/C5SC03530A
5. [5]
  Yoshino, Y.; Hayashi, Y.; Iwahama, T.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 1997, 62, 6810. doi: 10.1021/jo9708147
6. [6]
  Wolt, J. J. Org. Chem. 1975, 40, 1178. doi: 10.1021/jo00896a042
7. [7]
  Dick, A. R.; Sanford, M. S. Tetrahedron 2006, 62, 2439. doi: 10.1016/j.tet.2005.11.027
8. [8]
  Maison, W.; Weidmann, V. Synthesis 2013, 45, 2201. doi: 10.1055/s-0033-1338491
9. [9]
  Marwah, P.; Marwah, A.; Lardy, H. A. Green Chem. 2004, 6, 570. doi: 10.1039/b408974j
10. [10]
  Nakada, M.; Nakamura, A. Synthesis 2013, 45, 1421. doi: 10.1055/s-0033-1338426
11. [11]
  Recupero, F.; Punta, C. Chem. Rev. 2007, 107, 3800. doi: 10.1021/cr040170k
12. [12]
  Ren, L.; Gao, S. Chin J. Org. Chem. 2017, 37, 983(in Chinese).
13. [13]
  Arsenou, E. S.; Koutsourea, A. I.; Fousteris, M. A.; Nikolaropoulos, S. S. Steroids 2003, 5, 407.
14. [14]
  Jurado-Gonzalez, M.; Sullivan, A. C.; Wilson, J. R. H. Tetrahedron Lett. 2003, 22, 4283.
15. [15]
  Cao, H.; Zhu, B.; Yang, Y.; Xu, L.; Yu, L.; Xu, Q. Chin J. Catal. 2018, 39, 899. doi: 10.1016/S1872-2067(18)63050-5
16. [16]
  Liu, J.; Zhang, X.; Yi, H.; Liu, C.; Liu, R.; Zhang, H.; Zhuo, K.; Lei, A. Angew. Chem. Int. Ed. 2015, 54, 1261. doi: 10.1002/anie.201409580
17. [17]
  Hruszkewycz, D. P.; Miles, K. C.; Thiel, O. R.; Stahl, S. S. Chem. Sci. 2017, 8, 1282. doi: 10.1039/C6SC03831J
18. [18]
  Turra, N.; Neuenschwander, U.; Baiker, A.; Peeters, J.; Hermans, I. Chem. Eur. J. 2010, 16, 13226. doi: 10.1002/chem.201000489
19. [19]
  Serra, S. Eur. J. Org. Chem. 2015, 29, 6472.
20. [20]
  Tan, J.; Zheng, T.; Yu, Y.; Xu, K. RSC Adv. 2017, 7, 15176. doi: 10.1039/C7RA00352H
21. [21]
  Wu, X. F.; Gong, J. L.; Qi, X. Org. Biomol. Chem. 2014, 12, 5807. doi: 10.1039/C4OB00276H
22. [22]
  Yu, Y.; Humeidi, R.; Alleyn, J. R.; Doyle, M. P. J. Org. Chem. 2017, 82, 8506. doi: 10.1021/acs.joc.7b01163
23. [23]
  Zhang, W.; Wei, Q.; Lan, L.; Wu, A.; Yin, X.; Shen, L. Monatsh. Chem. 2016, 148, 357.
24. [24]
  Derdau, V. Tetrahedron Lett. 2004, 45, 8889. doi: 10.1016/j.tetlet.2004.09.165
25. [25]
  Rubottom, G. M.; Evain, E. J. Tetrahedron 1990, 46, 5055. doi: 10.1016/S0040-4020(01)87812-1
26. [26]
  Liu, M.; Chen, X.; Chen, T.; Yin, S. F. Org. Biomol. Chem. 2017, 15, 2507. doi: 10.1039/C7OB00062F
27. [27]
  Haber, F.; Weiss, J. P. R. Soc. A 1934, 147, 332.
28. [28]
  Goldstein, S.; Meyerstein, D. Acc. Chem. Res. 1999, 32, 547. doi: 10.1021/ar9800789
29. [29]
  Koppenol, W. H. Redox Rep. 2013, 6, 229.
1. [1]
  Jing JIN , Zhuming GUO , Zhiyin XIAO , Xiujuan JIANG , Yi HE , Xiaoming LIU . Tuning the stability and cytotoxicity of fac-[Fe(CO)₃I₃]^- anion by its counter ions: From aminiums to inorganic cations. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 991-1004. doi: 10.11862/CJIC.20230458
2. [2]
  Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V₂O₅/TiO₂ catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210
3. [3]
  Yi Zhang , Biao Wang , Chao Hu , Muhammad Humayun , Yaping Huang , Yulin Cao , Mosaad Negem , Yigang Ding , Chundong Wang . Fe–Ni–F electrocatalyst for enhancing reaction kinetics of water oxidation. Chinese Journal of Structural Chemistry, 2024, 43(2): 100243-100243. doi: 10.1016/j.cjsc.2024.100243
4. [4]
  Yi Herng Chan , Zhe Phak Chan , Serene Sow Mun Lock , Chung Loong Yiin , Shin Ying Foong , Mee Kee Wong , Muhammad Anwar Ishak , Ven Chian Quek , Shengbo Ge , Su Shiung Lam . Thermal pyrolysis conversion of methane to hydrogen (H₂): A review on process parameters, reaction kinetics and techno-economic analysis. Chinese Chemical Letters, 2024, 35(8): 109329-. doi: 10.1016/j.cclet.2023.109329
5. [5]
  Huixin Chen , Chen Zhao , Hongjun Yue , Guiming Zhong , Xiang Han , Liang Yin , Ding Chen . Unraveling the reaction mechanism of high reversible capacity CuP₂/C anode with native oxidation PO_x component for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(1): 109650-. doi: 10.1016/j.cclet.2024.109650
6. [6]
  Ruonan Yang , Jiajia Li , Dongmei Zhang , Xiuqi Zhang , Xia Li , Han Yu , Zhanhu Guo , Chuanxin Hou , Gang Lian , Feng Dang . Grain-refining Co_0.85Se@CNT cathode catalyst with promoted Li₂O₂ growth kinetics for lithium-oxygen batteries. Chinese Chemical Letters, 2024, 35(12): 109595-. doi: 10.1016/j.cclet.2024.109595
7. [7]
  Zizhuo Liang , Fuming Du , Ning Zhao , Xiangxin Guo . Revealing the reason for the unsuccessful fabrication of Li3Zr2Si2PO12 by solid state reaction. Chinese Journal of Structural Chemistry, 2023, 42(11): 100108-100108. doi: 10.1016/j.cjsc.2023.100108
8. [8]
  Liang Ma , Zhou Li , Zhiqiang Jiang , Xiaofeng Wu , Shixin Chang , Sónia A. C. Carabineiro , Kangle Lv . Effect of precursors on the structure and photocatalytic performance of g-C3N4 for NO oxidation and CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100416-100416. doi: 10.1016/j.cjsc.2024.100416
9. [9]
  Haojie Duan , Hejingying Niu , Lina Gan , Xiaodi Duan , Shuo Shi , Li Li . Reinterpret the heterogeneous reaction of α-Fe₂O₃ and NO₂ with 2D-COS: The role of SDS, UV and SO₂. Chinese Chemical Letters, 2024, 35(6): 109038-. doi: 10.1016/j.cclet.2023.109038
10. [10]
  Ping Lu , Baoyin Du , Ke Liu , Ze Luo , Abiduweili Sikandaier , Lipeng Diao , Jin Sun , Luhua Jiang , Yukun Zhu . Heterostructured In2O3/In2S3 hollow fibers enable efficient visible-light driven photocatalytic hydrogen production and 5-hydroxymethylfurfural oxidation. Chinese Journal of Structural Chemistry, 2024, 43(8): 100361-100361. doi: 10.1016/j.cjsc.2024.100361
11. [11]
  Ping Wang , Tianbao Zhang , Zhenxing Li . Reconstruction mechanism of Cu surface in CO2 reduction process. Chinese Journal of Structural Chemistry, 2024, 43(8): 100328-100328. doi: 10.1016/j.cjsc.2024.100328
12. [12]
  Yan Guo , Hongtao Bian , Le Yu , Jiani Ma , Yu Fang . Photochemical reaction mechanism of benzophenone protected guanosine at N7 position. Chinese Chemical Letters, 2025, 36(3): 109971-. doi: 10.1016/j.cclet.2024.109971
13. [13]
  Haixia Wu , Kailu Guo . Sulfur reduction reaction mechanism elucidated with in situ Raman spectroscopy. Chinese Chemical Letters, 2025, 36(6): 110654-. doi: 10.1016/j.cclet.2024.110654
14. [14]
  Zhiqiang Wang , Yajie Gao , Tianjun Wang , Wei Chen , Zefeng Ren , Xueming Yang , Chuanyao Zhou . Photocatalyzed oxidation of water on oxygen pretreated rutile TiO₂(110). Chinese Chemical Letters, 2025, 36(4): 110602-. doi: 10.1016/j.cclet.2024.110602
15. [15]
  Zhixiang Li , Zhirong Yang , Chang Yao , Bin Wu , Gang Qian , Xuezhi Duan , Xinggui Zhou , Jing Zhang . Efficient continuous synthesis of 2-hydroxycarbazole and 4-hydroxycarbazole in a millimeter scale photoreactor. Chinese Chemical Letters, 2024, 35(4): 108893-. doi: 10.1016/j.cclet.2023.108893
16. [16]
  Fengrui Yang , Debing Wang , Xinying Zhang , Jie Zhang , Zhichao Wu , Qiaoying Wang . Synergistic effects of peroxydisulfate on UV/O₃ process for tetracycline degradation: Mechanism and pathways. Chinese Chemical Letters, 2024, 35(10): 109599-. doi: 10.1016/j.cclet.2024.109599
17. [17]
  Qinwen Zheng , Xin Liu , Lintao Tian , Yi Zhou , Libing Liao , Guocheng Lv . Mechanism of Fenton catalytic degradation of Rhodamine B induced by microwave and Fe₃O₄. Chinese Chemical Letters, 2025, 36(4): 109771-. doi: 10.1016/j.cclet.2024.109771
18. [18]
  Yubang Li , Xixi Hu , Daiqian Xie . The microscopic formation mechanism of O + H2 products from photodissociation of H2O. Chinese Journal of Structural Chemistry, 2024, 43(5): 100274-100274. doi: 10.1016/j.cjsc.2024.100274
19. [19]
  Xin Li , Wanting Fu , Ruiqing Guan , Yue Yuan , Qinmei Zhong , Gang Yao , Sheng-Tao Yang , Liandong Jing , Song Bai . Nucleophiles promotes the decomposition of electrophilic functional groups of tetracycline in ZVI/H₂O₂ system: Efficiency and mechanism. Chinese Chemical Letters, 2024, 35(10): 109625-. doi: 10.1016/j.cclet.2024.109625
20. [20]
  Xiao-Hong Yi , Chong-Chen Wang . Metal-organic frameworks on 3D interconnected macroporous sponge foams for large-scale water decontamination: A mini review. Chinese Chemical Letters, 2024, 35(5): 109094-. doi: 10.1016/j.cclet.2023.109094

Get Citation

PDF

XML

Metrics

PDF Downloads(4)
Abstract views(823)
HTML views(104)

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