中华医学超声杂志

应用化学 ›› 2010, Vol. 27 ›› Issue (03): 267-271.DOI: 10.3724/SP.J.1095.2010.90235

• 研究论文 • 上一篇    下一篇

负载型二乙酰氧碘苯与功能离子液体协同氧化醇为醛酮

朱晨杰,魏运洋*,计磊,张倩   

  1. (南京理工大学化工学院 南京 210094)
  • 收稿日期:2009-03-31 修回日期:2009-06-02 出版日期:2010-03-10 发布日期:2010-03-10
  • 通讯作者: 魏运洋,男,教授,博士生导师; E-mail:yunyang@mail.njust.edu.cn; 研究方向：有机合成

Oxidation of Alcohols to Corresponding Aldehydes and Ketones with Polystyrene-supported Hypervalent Iodine Oxidant and Task-Specific Ionic Liquid

ZHU Chen-Jie, WEI Yun-Yang*, JI Lei, ZHANG Qian   

  1. (Institute of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094)
  • Received:2009-03-31 Revised:2009-06-02 Published:2010-03-10 Online:2010-03-10

PDF

1285

被引次数

5 | 1

摘要：

将聚苯乙烯树脂先碘化再乙酰基化，制得了负载型二乙酰氧碘苯(diacetoxyiodo polystyrene，PS-DIB)作为氧化剂。2，2，6，6-四甲基-N-氧自由基哌啶醇(2，2，6，6-tetramethyl-piperidin-4-ol-N-oxyl，TEMPO)与1，4-二溴丁烷反应生成4-溴丁氧基-2，2，6，6-四甲基-哌啶-1-氧化物，再与N-甲基咪唑发生季铵化反应，生成的溴化季铵盐与四氟硼酸钠进行离子交换制得氟硼酸型2，2，6，6-四甲基-N-氧自由基哌啶负载离子液体TEMPO-IL。室温下，以离子液体1-甲基-3-丁基咪唑四氟硼酸盐([bmim]BF4)为溶剂，PS-DIB为氧化剂，TEMPO-IL为催化剂，选择性协同氧化各种醇为相应的醛或酮。在实验条件范围内未检测到羧酸副产物。氧化剂、催化剂和溶剂均可循环使用，在苯甲醇的氧化中，经5次循环，反应的转化率和收率均保持基本不变。

关键词: 聚苯乙烯，功能离子液体，氧化，醇

Abstract:

A selective and mild PS-DIB (Diacetoxyiodo polystyrene)/ionic-liquid immobilized TEMPO catalytic oxidation procedure of alcohols to the corresponding aldehydes and ketones in ionic liquid [bmim]BF4 at room temperature was developed. The oxidant PS-DIB was prepared via Iodation and acetylation of polystyrene resin. For the preparation of the ionic-liquid immobilized TEMPO(TEMPO-IL) catalyst, 4-(2,2,6,6-Tetramethyl-1-oxyl-4-piperidoxyl)butyl bromide was first synthesized from 2,2,6,6-tetramethyl-piperidin-4-ol-N-oxyl (TEMPO) and 1,4-dibromobutane. The TEMPO-IL was then obtained via the quaternization of 1-methyl-1H-imidazole with 4-(2,2,6,6-Tetramethyl-1-oxyl-4-piperidoxyl)butyl bromide followed by ion exchange with NaBF4. The PS-DIB/TEMPO-IL catalytic system applied to the oxidation of a variety of alcohols to the corresponding aldehyde or ketones selectively. No carboxylic acid was detected under the experimental conditions. In the case of the oxidation of benzyl alcohol, the oxidant, catalyst and the solvent were recovered and reused for 5 times with no decreases of benzyl alcohol conversion and product yield.

Key words: polystyrene, task-specific ionic liquids, oxidation, alcohol

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