In situ multinuclear solid-state NMR spectroscopy study of Beckmann rearrangement of cyclododecanone oxime in ionic liquids: The nature of catalytic sites

被引：12
作者：
Blasco, T. [1 ]
Corma, A. [1 ]
Iborra, S. [1 ]
Lezcano-Gonzalez, I. [1 ]
Monton, R. [1 ]
机构：
[1] Univ Politecn Valencia, Inst Tecnol Quim UPV CSIC, Consejo Super Invest Cient, Valencia 46022, Spain
来源：
JOURNAL OF CATALYSIS | 2010年 / 275卷 / 01期
关键词：
Ionic liquids; Beckmann rearrangement; Cyclododecanone oxime; 1-Butyl-3-methylimidazolium hexafluorophosphate; 1-Butyl-4-methylpyridinium hexafluorophosphate; 1-Butyl-2,3-dimethylimidazolium hexafluorophosphate; 1-Butyl-3-methylimidazolium tetrafluoroborate; Hydrofluoric acid; 'In situ' solid-state NMR; N-15-CYCLOHEXANONE OXIME; EPSILON-CAPROLACTAM; ACTIVE-SITES; CYCLOHEXANONE; ZEOLITES; CHLORIDE; CHALLENGES; KETOXIMES; SOLVENTS; SALTS;
D O I：
10.1016/j.jcat.2010.07.016
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
The Beckmann rearrangement of cyclododecanone oxime into omega-laurolactam has been investigated in four ionic liquids: 1-butyl-3-methylimidazolium hexafluorophosphate and tetrafluoroborate ([C(4)mim]+PF6-, [C(4)mim]+BF4-), and 1-butyl-2,3-dimethylimidazolium and 1-butyl-4-methylpyridinium hexafluorophosphates ([C(4)mpyr]+PF6-, [C(4)m(2)im]+PF6-), in a batch reactor as well as by 'in situ' multinuclear solid-state NMR spectroscopy. The Beckmann rearrangement reaction of cyclododecanone oxime takes place in [C(4)mim]+PF6- and [C(4)mpyr]+PF6- with excellent activity and selectivity, while practically null activity is observed in [C(4)m(2)im]+PF6- and [C(4)mim]+BF4-. The results obtained indicate that a very low level of hydrolysis of the PF6- anion in [C(4)mim]+PF6- and [C(4)mpyr]+PF6- occurs under reaction conditions (130 degrees C), and the HF formed at the level of ppm acts as catalyst in the Beckmann rearrangement with excellent conversion and selectivity. (C) 2010 Elsevier Inc. All rights reserved.
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页码：78 / 83
页数：6
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