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›› 2004, Vol. 4 ›› Issue (3): 261-264.

• 绿色化学与技术专栏 • 上一篇    下一篇

[bmim][BF4]离子液体中PCl3催化的液相贝克曼重排

张伟,吴巍,张树忠,闵恩泽   

  1. 中国石油化工股份有限公司石油化工科学研究院十室
  • 出版日期:2004-06-20 发布日期:2004-06-20

Two-phase Beckmann Rearrangement of Cyclohexanone Oxime for Preparing e-Caprolactam in [bmim][BF4] Ionic Liquids Using PCl3 as Catalyst

ZHANG Wei,WU Wei,ZHANG Shu-zhong　,MIN En-ze   

  1. Research Institute of Petroleum Processing
  • Online:2004-06-20 Published:2004-06-20

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被引次数

33

摘要： 在1-丁基-3-甲基咪唑四氟硼酸盐([bmim][BF4])与甲苯组成的两相体系中，以三氯化磷(PCl3)为催化剂，实现了由环己酮肟制备己内酰胺的液相贝克曼重排反应，两相体系有利于反应控制和体系取热. 研究了环己酮肟用量、PCl3用量、反应时间和反应温度对重排效果的影响. 优化反应条件为: 2 ml [bmim][BF4], 5 ml甲苯, 0.3 ml PCl3, 5 ml 2 mol/L环己酮肟-甲苯溶液, 90oC, 反应时间10~30 min. 此时，环己酮肟转化率达98.96%，生成己内酰胺的选择性达87.30%，PCl3催化转化数达2.88. 生成的大部分己内酰胺在离子液体相.

关键词: 离子液体, 贝克曼重排, 己内酰胺, 环己酮肟, 三氯化磷, 选择性

Abstract: The Beckmann rearrangement of cyclohexanone oxime was effectively realized to prepare e-caprolactam by using phosphorous trichloride (PCl3) as catalyst in a two-phase system composed of 1-n-butyl-3- methylimidazolium tetrafluoroborate ([bmim][BF4]) ionic liquids and toluene. The system of two-phase facilitates the control of the reaction and the removal of reaction heat. The effects of the amount of cyclohexanone oxime and PCl3, reaction temperature and reaction time on the conversation of cyclohexanone oxime, selectivity of e-caprolactam and turnover numbers (TON) of PCl3 were studied. The optimized conditions were 2 ml [bmim][BF4], 5 ml toluene, 0.3 ml PCl3, 5.0 ml 2.0 mol/L cyclohexanone oxime, 90oC and 10~30 min. At the same time, the conversation of cyclohexanone oxime could reach 98.96%, the selectivity of e-caprolactam could reach 87.30% and the TON of PCl3 could reach 2.88. Most of the e-caprolactam (>90%) existed in the ionic liquid phase.

Key words: ionic liquids, Beckmann rearrangement, e-caprolactam, cyclohexanone oxime, phosphorous trichloride, selectivity