Citation: Zhi Xue, Xianzhi Dai, Lie Yu, Zisong Yang, Yiyan Hong, Youqi Pu, Yan Zhou, Fei Huang. Pd/C催化Suzuki反应合成4-联苯甲酸[J]. University Chemistry, ;2022, 37(5): 211004. doi: 10.3866/PKU.DXHX202110046 shu

Pd/C催化Suzuki反应合成4-联苯甲酸

Zhi Xue ^1,, ,
Xianzhi Dai ¹ ,
Lie Yu ¹ ,
Zisong Yang ¹ ,
Yiyan Hong ¹ ,
Youqi Pu ¹ ,
Yan Zhou ¹ ,
Fei Huang ²

1.
College of Resources & Environment, Aba Teachers University, Wenchuan 623002, Sichuan Province, China;
2.
School of Resource and Environmental Engineering, Yibin University, Yibin 644000, Sichuan Province, China

Corresponding author: Zhi Xue, chemxz@163.com
Received Date: 15 October 2021

通过芳基卤代物和芳基硼酸合成联苯类化合物的Suzuki-Miyaura偶联反应被广泛应用于天然产物，药物和功能材料的合成。然而目前本科教学中极少有相关实验，主要是由于传统的Suzuki反应条件通常需要昂贵的含配体Pd催化剂，反应溶剂大多含有诸如甲苯或者1，4-二氧六环等有毒害溶剂，反应过程需要惰性气体氛围，且大多需在加热反应8 h以上。这些限制极大地阻碍了本科生开展这一重要的有机化学实验。本文介绍了改进的Suzuki反应条件：无配体Pd/C作为催化剂，乙醇和水的混合溶剂作为反应溶剂，并且室温搅拌半小时反应即可结束，反应全程敞口需要空气（氧气）的辅助而不是惰性氛围。在此条件下，以苯硼酸与4-溴苯甲酸为原料，碳酸钾作为碱，高效合成了4-联苯甲酸。相比传统Suzuki反应条件下催化剂均为一次性使用，不可回收，本实验中回收的Pd/C催化剂可循环使用5次以上而几无活性损失。本实验项目从成本，可操作性，绿色环保等角度为本科生熟悉Suzuki反应提供了可能。
- 4-Bibenzoic acid,
- Suzuki-Miyaura reaction,
- Pd/C,
- Air atmosphere,
- Recycle and reuse
1. [1]
  Navarro, O.; Kelly, R. A.; Nolan, S. P. J. Am. Chem. Soc. 2003, 125, 16194.
2. [2]
  Barder, T. E.; Walker, S. D.; Martinelli, J. R.; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, 4685.
3. [3]
4. [4]
5. [5]
6. [6]
7. [7]
8. [8]
  Dai, J.; Lu, D.; Ye, T.; Yu, S.; Cheng, X. J. Chem. Educ. 2019, 96, 2672.
9. [9]
  Costa, N. E.; Pelotte, A. L.; Simard, J. M.; Syvinski, C. A.; Deveau, A. M. J. Chem. Educ. 2012, 89, 1064.
10. [10]
  Hamilton, A. E.; Buxton, A. M.; Peeples, C. J.; Chalker, J. M. J. Chem. Educ. 2013, 90, 1509.
11. [11]
  Hill, N. J.; Bowman, M. D.; Esselman, B. J.; Byron, S. D.; Kreitinger, J.; Leadbeater, N. E. J. Chem. Educ. 2014, 91, 1054.
12. [12]
  Hie, L.; Chang, J. J.; Garg, N. K. J. Chem. Educ. 2015, 92, 571.
13. [13]
  Soares, P.; Fernandes, C.; Chavarria, D.; Borges, F. J. Chem. Educ. 2015, 92, 575.
14. [14]
  Reyne, P.; Angus, O.; Smith, J. A.; Bissember, A. C. J. Chem. Educ. 2018, 95, 2081.
15. [15]
  Lee, J.; Schmink, J. R.; Berritt, S. J. Chem. Educ. 2020, 97, 538.
16. [16]
  Ang, J. J. Chem. Educ. 2020, 98, 203.
17. [17]
  Koudehi, M. F.; Zibaseresht, R. J. Chem. Educ. 2020, 97, 3822.
18. [18]
  Huang, Z.; Yan, X.; Jiang, L.; Jiang, H. Chin. J. Catal. 2010, 31, 90.
19. [19]
  Kitamura, Y.; Sako, S.; Udzu, T.; Tsutsui, A.; Maegawa, T.; Monguchi, Y.; Sajiki, H. Chem. Commun. 2007, 39, 5069.
20. [20]
  Khedkar, M. V.; Tambade, P. J.; Qureshi, Z. S.; Bhanage, B. M. Eur. J. Org. Chem. 2010, 2010, 6981.
21. [21]
22. [22]
  Rao, X.; Liu, C.; Xing, Y.; Fu, Y.; Qiu, J.; Jin, Z. Asian J. Org. Chem. 2013, 2, 514.
23. [23]
  Liu, C.; Liu, C.; Li, X. M.; Gao, Z. M.; Jin, Z. L. Chin. Chem. Lett. 2016, 5, 631.
24. [24]
25. [25]
  Adamo, C.; Amatore, C.; Ciofini, I.; Jutand, A.; Lakmini, H. J. Am. Chem. Soc. 2006, 128, 6829.
26. [26]
  Corma, A.; García, H.; Leyva, A. J. Catal. 2006, 240, 87.
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