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

Abstract

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

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.

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.

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