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)

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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
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