Chin. J. Org. Chem. ›› 2019, Vol. 39 ›› Issue (4): 1122-1128.DOI: 10.6023/cjoc201809001 Previous Articles     Next Articles

Articles

氢键驱动的二苯甲酮肟Beckmann重排反应研究

冯一格, 叶浙高, 郝仕油   

  1. 浙江师范大学行知学院 金华 321004
  • 收稿日期:2018-09-02 修回日期:2018-10-27 出版日期:2019-04-25 发布日期:2018-12-05
  • 通讯作者: 郝仕油 E-mail:sky54@zjnu.cn
  • 基金资助:

    国家自然科学基金(No.21876158)资助项目.

Hydrogen Bond Driven Beckmann Rearrangement of Diphenyl-ketoxime

Feng Yige, Ye Zhegao, Hao Shiyou   

  1. Xingzhi College, Zhejiang Normal University, Jinhua 321004
  • Received:2018-09-02 Revised:2018-10-27 Online:2019-04-25 Published:2018-12-05
  • Contact: 10.6023/cjoc201809001 E-mail:sky54@zjnu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (21876158).

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℃.

Key words: hydrogen bond, diphenyl-ketoxime, Beckmann rearrangement, amino functionalized mesoporous silica, N-benzophenamide