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

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

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. 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

收稿日期:2008-10-19 修回日期:2009-10-14 出版日期:2009-12-28 发布日期:2009-12-28
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)

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

YANG Min^1,2, PENG Qianrong³, XIE Rugang¹, SONG Guangfu², LAN Jingbo¹, YOU Jinsong¹

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)

摘要/Abstract

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

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

杨敏, 彭黔荣, 谢如刚, 宋光富, 兰静波, 游劲松. Homogeneous and Heterogeneous Performances of Pyridinium Ionic Liquids in the Allylic Oxidation of Ionone-like Dienes[J]. , 2009, 17(6): 967-975.

YANG Min, PENG Qianrong, XIE Rugang, SONG Guangfu, LAN Jingbo, YOU Jinsong. Homogeneous and Heterogeneous Performances of Pyridinium Ionic Liquids in the Allylic Oxidation of Ionone-like Dienes[J]. , 2009, 17(6): 967-975.

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

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

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