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离子液体介入的均苯三甲酸氧钒催化氧化异丁香酚制香草醛

黄红梅1,2,肖毅1,2,杨晰雅1,边文欢1,尹笃林1,2*,毛丽秋1,2   

  1. (1.石化新材料与资源精细利用国家地方联合工程实验室;
    2.化学生物学及中药分析教育部重点实验室,湖南师范大学化学化工学院 长沙 410081)
  • 收稿日期:2013-10-14 修回日期:2014-01-10 出版日期:2014-08-10 发布日期:2014-08-10
  • 通讯作者: 尹笃林,教授; Tel:0731-88872576; Fax:0731-88872531; E-mail:dulinyin@126.com; 研究方向:有机催化合成
  • 基金资助:
    国家自然科学基金(20572021,20805014)湖南省教育厅科学研究基金(11C0809,12B077,12CY004)资助项目

Ionic Liquid-mediated Catalytic Oxidation of Isoeugenol to Vanillin via Oxovanadium 1,3,5-Benzenetricarboxylate

HUANG Hongmei1,2, XIAO Yi1,2, YANG Xiya1, BIAN Wenhuan1, YIN Dulin1,2*, MAO Liqiu1,2   

  1. (1.National & Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of Resources;
    2.Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research,Ministry of Education,
    College of Chemistry and Chemical Engineering,Hunan Normal University,Changsha 410081,China)
  • Received:2013-10-14 Revised:2014-01-10 Published:2014-08-10 Online:2014-08-10
  • Contact: Yin Dulin

摘要: 合成了系列均苯三甲酸氧钒配合物催化剂,并进行了FT-IR、紫外-可见漫反射光谱(DR UV-Vis)及TG表征。 系统考察了催化剂、不同种类的离子液体助剂、离子液体用量和反应时间等因素对异丁香酚氧化制备香草醛的影响。 结果表明,n(VO2+)∶n(BTC(均苯三甲酸根))=1∶1时制备的催化剂VO(BTC)-1性能较佳。 以VO(BTC)-1为催化剂、氯化1-十二烷基-3-甲基咪唑([C12mim]Cl)为助剂、丙酮为介质,当n(异丁香酚)∶n(H2O2)∶n([C12mim]Cl)=1∶2∶0.01时20 ℃反应24 h,异丁香酚可转化完全,香草醛收率达到87.2%。 基于离子液体介入的催化剂光谱特征及反应结果,推测[C12mim]Cl/VO(BTC)-1与H2O2形成了高效的氧化反应体系从而有利于异丁香酚的温和转化。

关键词: 均苯三甲酸氧钒, 香草醛, 催化氧化, 离子液体, 异丁香酚

Abstract: A series of oxovanadium 1,3,5-benzenetricarboxylate complex catalysts was prepared and characterized by FT-IR, diffuse reflectance UV-Vis(DR UV-Vis) and TG, respectively. The effects of catalyst, promoter such as ionic liquid, ionic liquid amount and reaction time on the oxidation of isoeugenol to vanillin were investigated systematically. VO(BTC)-1 with a molar ratio of VO2+ and BTC(1,3,5-benzenetricarboxylate) as 1∶1 exhibits better catalytic performance. Complete conversion of isoeugenol and 87.2% yield of vanillin are achieved using VO(BTC)-1 as catalyst, 1-dodecyl-3-methylimidazolium chloride([C12mim]Cl) as additive with the molar ratio of isoeugenol, H2O2 and [C12mim]Cl as 1∶2∶0.01 after 24 h reaction at 20 ℃ in acetone. The formation of a highly effective oxidation system from [C12mim]Cl/VO(BTC)-1 and H2O2 is beneficial in the mild conversion of isoeugenol, as indicated by spectral characterization and the reaction results.

Key words: oxovanadium benzenetricarboxylate, vanillin, catalytic oxidation, ionic liquid, isoeugenol

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