Theoretical study on vapour phase Beckmann rearrangement of cyclohexanone oxime over a high silica MFI zeolite

被引：34

作者：

Ishida, M

Suzuki, T

Ichihashi, H

Shiga, A

机构：

[1] Sumitomo Chem Co Ltd, Tsukuba Res Lab, Tsukuba, Ibaraki 3003294, Japan

[2] Sumitomo Chem Co Ltd, Basic Chem Res Lab, Sobiraki, Niihama 7925821, Japan

来源：

CATALYSIS TODAY | 2003年 / 87卷 / 1-4期

关键词：

cyclohexanone; Beckmann rearrangement; double numerical polarization;

D O I：

10.1016/j.cattod.2003.10.021

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

We have studied an activation mechanism of cyclohexanone oxime in a cavity of high silica MFI zeolite by using PIO analysis proposed by Fujimoto et al. DFT calculation reveals that the bond length of N-OH becomes longer when water coordinates on oxygen of oxime. The PIO clearly shows out-of-phase interaction between N and O. This out-of-phase interaction is also observed in the PIO of oxime/MFI zeolite cluster model and weakens the N-O bond. Hydrogen bond of Si-OH of nest silanols to oxime is a trigger of vapour phase Beckmann rearrangement. (C) 2003 Elsevier B.V. All rights reserved.

引用

页码：187 / 194

页数：8

共 10 条

[1] A THEORETICAL-STUDY OF OLEFIN INSERTIONS INTO TI-C AND TI-H BONDS - AN ANALYSIS BY PAIRED INTERACTING ORBITALS [J].