Homogeneous and Heterogeneous Performances of Pyridinium Ionic Liquids in the Allylic Oxidation of Ionone-like Dienes  

作　　者：杨敏 彭黔荣 谢如刚 宋光富 兰静波 游劲松 

机构地区：[1]Department of Chemistry, Sichuan University, Chengdu 610064, China [2]School of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550003, China [3]Technology Center, China Tobacco Guizhou Industry Co., Ltd., Guiyang 550003, China

出　　处：《Chinese Journal of Chemical Engineering》2009年第6期967-975,共9页中国化学工程学报（英文版）

基　　金：Supported by the National Natural Science Foundation of China （20472057）

摘　　要：The combination of relatively low-cost ionic liquids, simple copper salt, and terminal oxidant tert-butyl hydroperoxide provided an efficient and environmentally friendly approach to the preparation of ionone-like dienones. Six pyridinium ionic liquids were evaluated in allylic oxidation of α-ionone and β-ionone. The 60%-70% yields of 3-oxo-α-ionone were obtained with 0.02 0.20 mmol of CuCl2·2H2O as catalyst, 3-5 mmol of tert-butyl hydroperoxide as oxidant and 1 g of [Bpy]PF6 as solvent for 4-20 h at 60℃. The facile recovery and recycle of catalyst were also achieved. More significantly, peculiar phase behaviors of [Bpy]PF6 and [Epy]PF6 offered the catalytic system advantages of homogeneous reaction and heterogeneous separation. Scanning electron microscope （SEM） images of [Bpy]PF6 provided evidences for the behaviors. Transmission electron microscope （TEM） micrographs showed copper salt nanoparticles catalyst formed and stabilized in pyridinium ionic liquids.相对便宜的离子的液体，简单的铜盐，和终端氧化剂 tert 丁基水疗院过氧化物的联合提供了一有效并且环境联盟者象 ionone 一样的准备的友好途径死没有。六 pyridinium 离子的液体在 &#x3b1 的 allylic 氧化被评估； -ionone 和 &#x3b2； -ionone。60% &#x2013 ；3-oxo- &#x3b1 的70%收益； -ionone 与 0.02 &#x2013 被获得； CuCl ₂&#xb7;2H<sub>2</sub 的 0.20 mmol > O 是催化剂， 3 &#x2013 ；tert丁基水疗院过氧化物的 5 mmol 作为氧化剂和 1 g [ Bpy ] PF ₆作为为 4 &#x2013 的溶剂；在 60 &#xb0 的 20 h ； C 。灵巧的恢复并且催化剂再循环也被完成。更显著地，古怪阶段行为[Bpy ] PF ₆ 并且[Epy ] PF ₆ 提供了同类的反应和异构的分离的催化系统优点。扫描电子显微镜(SEM ) 图象[Bpy ] PF ₆ 为行为提供了证据。传播电子显微镜(TEM ) 显微图显示出在 pyridinium 形成并且稳定离子的液体的铜盐 nanoparticles 催化剂。

关 键 词：allylic oxidation ionone-like dienone copper salt nanoparticle tert-butyl hydroperoxide pyridinium ionic liquid 

分 类 号：TQ430.77[化学工程] TQ655