Citation: Feng Yige, Ye Zhegao, Hao Shiyou. Hydrogen Bond Driven Beckmann Rearrangement of Diphenyl-ketoxime[J]. Chinese Journal of Organic Chemistry, ;2019, 39(4): 1122-1128. doi: 10.6023/cjoc201809001 shu

Hydrogen Bond Driven Beckmann Rearrangement of Diphenyl-ketoxime

Xingzhi College, Zhejiang Normal University, Jinhua 321004

Corresponding author: Hao Shiyou, sky54@zjnu.cn
Received Date: 2 September 2018
Revised Date: 27 October 2018
Available Online: 5 April 2018
Fund Project: the National Natural Science Foundation of China 21876158Project supported by the National Natural Science Foundation of China (21876158)

Figures(12)

Based on fully analyzing the mechanism of Beckmann rearrangement reaction, protonated amino functional mesoporous silica materials HAF-SBA-15 were obtained via acidizing amino functional mesoporous silica. The binding force between hydroxamic hydroxyl group and N was synergistically weakened by the coordination bond formed by proton hydrogen in HAF-SBA-15, lone pair electrons in hydroxyl hydroxoxoxime and hydrogen bonds formed between N, H and O. It synergistically weakenef the binding force between oxime hydroxyl and N, accelerated the departure of oxime hydroxyl and the formation of carbon positive ions, , and promoted the Beckmann rearrangement reaction. Catalyzed by HAF-SBA-15, N-benzo-phenamide was synthesized via the Beckmann rearrangement of diphenyl-ketoxime. The results showed that the conversion rate of diphenyl-ketoxime is high and the obtained N-benzophenamide is pure. Furthermore, effect of solvent type, reaction temperature, and catalyst dosage on the Beckmann rearrangement of diphenyl-ketoxime was investigated, and the optimum reaction conditions were obtained. The results illustrated that the optimum reaction conditions are mild because Beckmann rearrangement of diphenyl-ketoxime was efficiently carried out at 50℃.
- hydrogen bond,
- diphenyl-ketoxime,
- Beckmann rearrangement,
- amino functionalized mesoporous silica,
- N-benzophenamide
1. [1]
  Zhang, W. Q.; Zheng, Y.; Ma, L. Textbook of Organic Chemistry, 5 ed., Higher Education Press, Beijing, 2014, p. 385 (in Chinese).
2. [2]
  Lin, C. R.; Yu, L. J.; Li S. H.; Karton, A. Chem. Phys. Lett. 2016, 659, 100. doi: 10.1016/j.cplett.2016.07.018
3. [3]
  Hilmey, D. G.; Paquette, L. A. Org. Lett. 2005, 7, 2067. doi: 10.1021/ol050669g
4. [4]
  Elango, K.; Srirambalaji, R.; Anantharaman, G. Tetrahedron Lett. 2007, 48, 9059. doi: 10.1016/j.tetlet.2007.10.051
5. [5]
  Liu, L. F.; Liu, H.; Pi, H. J.; Yang, S.; Yao, M.; Du, W. T.; Deng, W. P. Synth. Commun. 2011, 41, 553. doi: 10.1080/00397911003629416
6. [6]
  Mahajan, S.; Sharma, B.; Kapoor, K. K. Tetrahedron Lett. 2015, 56, 1915. doi: 10.1016/j.tetlet.2015.02.110
7. [7]
  Mao, D.; Long, Z. Y.; Zhou, Y.; Li, J.; Wang, X. C.; Wang, J. RSC Adv. 2014, 4, 15635. doi: 10.1039/c4ra00552j
8. [8]
  Boero, M.; Ikeshoji, T.; Liew, C. C.; Terakura, K.; Parrinello, M. J. Am. Chem. Soc. 2004, 126, 6280. doi: 10.1021/ja049363f
9. [9]
  Kumar, R.; Enjamuri, N.; Pandey, J. K.; Sen, D.; Mazumder, S.; Bhaumik, A.; Chowdhury, B. Appl. Catal. A 2015, 497, 51. doi: 10.1016/j.apcata.2015.02.044
10. [10]
  Zhao, D.; Huo, Q.; Feng, J.; Chmelka, B. F.; Stucky, G. D. J. Am. Chem. Soc. 1998, 120, 6024. doi: 10.1021/ja974025i
11. [11]
  Wang, X.; Lin, K. S. K.; Chan, J. C. C.; Cheng, S. J. Phys. Chem. B 2005, 109, 1763. doi: 10.1021/jp045798d
12. [12]
  Chong, A. S. M.; Zhao, X. S. J. Phys. Chem. B 2003, 107, 12650. doi: 10.1021/jp035877+
13. [13]
  Llusar, M.; Monros, G.; Roux, C.; Pozzo, J. L.; Sanchez, C. J. Mater. Chem. 2003, 13, 2505. doi: 10.1039/B304479N
14. [14]
  Potter, M. E.; Malley, A. J. O.; Chapman, S.; Chapman, S.; Kezina, J. ACS Catal. 2017, 7, 2926. doi: 10.1021/acscatal.6b03641
15. [15]
  Zeng, Z. Q., Zeng, H. Q. Organic Chemistry Experiment, Higher Education Press, Beijing, 2005, p. 33 (in Chinese).
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