SCI和EI收录∣中国化工学会会刊

›› 2009, Vol. 17 ›› Issue (6): 967-975.

• CATALYSIS, KINETICS AND REACTORS • Previous Articles     Next Articles

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

YANG Min1,2, PENG Qianrong3, XIE Rugang1, SONG Guangfu2, LAN Jingbo1, YOU Jinsong1   

  1. 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
  • Received:2008-10-19 Revised:2009-10-14 Online:2009-12-28 Published:2009-12-28
  • Supported by:
    Supported by the National Natural Science Foundation of China (20472057)

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

杨敏1,2, 彭黔荣3, 谢如刚1, 宋光富2, 兰静波1, 游劲松1   

  1. 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
  • 通讯作者: HUANG Guolin,E-mail:pengqr@publish.gz.cn;XIE Rugang,schemorg@mail.cninfo.net
  • 基金资助:
    Supported by the National Natural Science Foundation of China (20472057)

Abstract: 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.

Key words: allylic oxidation, ionone-like dienone, copper salt nanoparticle, tert-butyl hydroperoxide, pyridinium ionic liquid

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.

关键词: allylic oxidation, ionone-like dienone, copper salt nanoparticle, tert-butyl hydroperoxide, pyridinium ionic liquid