Mechanistic Insight into Self-Propagation of Organo-Mediated Beckmann Rearrangement: A Combined Experimental and Computational Study

作者：An, Na; Tian, Bo-Xue; Pi, Hong-Jun; Eriksson, Leif A.; Deng, Wei-Ping^*

来源：Journal of Organic Chemistry, 2013, 78(9): 4297-4302.

DOI：10.1021/jo400278c

• CYCLOHEXANONE-OXIME
• SUPERCRITICAL WATER
• EPSILON-CAPROLACTAM
• NONCATALYTIC BECKMANN
• EFFICIENT CATALYST
• CYANURIC CHLORIDE
• KETOXIMES
• MILD
• LACTAMS
• LIQUID

Organo-mediated Beckmann rearrangement in the liquid phase, which has the advantage of high efficiency and straightforward experimental procedures, plays an important role in e synthesis of amides from oximes. However, the catalytic mechanisms of these organic-based promoters are still not well understood. In this work, we report a combined experimental and computational study on the mechanism of Beckmann rearrangement mediated by Organic-based promoters, using TsCl as an example. A novel self-propagating cycle is proposed, and key intermediates of this self-propagating cycle are confirmed by both experiments and DFT calculations. In addition, the reason why cyclohexanone oxime is not a good substrate of the organo-mediated Beckmann rearrangement is discussed, and a strategy for improving the yield is proposed.

• 出版日期2013-5-3
• 单位华东理工大学