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Citation: Jiabo Huang, Quanxin Li, Zhongyan Cao, Li Dang, Shaofei Ni. Elucidating the Mechanism of Beckmann Rearrangement Reaction Using Quantum Chemical Calculations[J]. University Chemistry, ;2025, 40(3): 153-159. doi: 10.12461/PKU.DXHX202405172 shu

Elucidating the Mechanism of Beckmann Rearrangement Reaction Using Quantum Chemical Calculations

Jiabo Huang ¹ ,
Quanxin Li ¹ ,
Zhongyan Cao ² ,
Li Dang ^1,, ,
Shaofei Ni ^1,,

1.
Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, College of Chemistry & Chemical Engineering, Shantou University, Shantou 515063, Guangdong Province, China;
2.
College of Chemistry and Molecular Sciences, Henan University, Kaifeng 475004, Henan Province, China

Corresponding author: Li Dang, Shaofei Ni,
Received Date: 27 May 2024
Revised Date: 2 September 2024

Beckmann rearrangement is a classical reaction in the courses of organic chemistry. However, mainstream textbooks often lack detailed explanations of its reaction mechanism, leaving students with a superficial understanding. This study investigates the Beckmann rearrangement mechanism of three types of ketoxime structures under two different proton sources using quantum chemical calculations. The detailed comparison and analysis provide insights into rearrangement process, including the migration rules of cis- and trans-ketoxime structures. Additionally, the electronic structures of the σ-type and π-type nitrilium ion intermediates are analyzed through frontier molecular orbital theory. This work aims to deepen students’ understanding of Beckmann rearrangement and introduce them to the application of theoretical computational chemistry in studying chemical reactions and their underlying mechanisms.
- Beckmann rearrangement,
- DFT calculations,
- Reaction mechanism
1. [1]
2. [2]
3. [3]
4. [4]
5. [5]
6. [6]
  Clayden, J.; Greeves, N.; Warren, S. G. Organic Chemistry, 2nd ed.; Oxford University Press: Oxford, UK, 2012, pp. 945-949.
7. [7]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; et al. Gaussian 16, Revision A.03; Gaussian Inc.: Wallingford CT, 2016.
8. [8]
  Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, 1200.
9. [9]
  Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
10. [10]
  Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
11. [11]
  Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623.
12. [12]
  Stefan G.; Jens, A.; Stephan, E.; Helge, K. J. Chem. Phys. 2010, 132, 154104.
13. [13]
  Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378.
14. [14]
  Yamabe, S.; Minato, T. Bull. Chem. Soc. Jpn. 1993, 66, 3339.
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