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

doi:10.3724/SP.J.1095.2014.30510

摘要/Abstract

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

中图分类号:

黄红梅, 肖毅, 杨晰雅, 边文欢, 尹笃林, 毛丽秋. 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[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30510.

HUANG Hongmei1,2, XIAO Yi1,2, YANG Xiya1, BIAN Wenhuan1, YIN Dulin1,2*, MAO Liqiu1,2. Ionic Liquid-mediated Catalytic Oxidation of Isoeugenol to Vanillin via Oxovanadium 1,3,5-Benzenetricarboxylate[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30510.

参考文献

[1] Adilina I B,Hara T,Ichikuni N,et al. Oxidative Cleavage of Isoeugenol to Vanillin under Molecular Oxygen Catalysed by Cobalt Porphyrin Intercalated into Lithium Taeniolite Clay[J]. J Mol Catal A:Chem,2012,361/362]:72-79.

[2] Bjrsvik H R,Liguori L. Organic Processes to Pharmaceutical Chemicals Based on Fine Chemicals from Lignosulfonates[J]. Org Process Res Dev,2002,6]:279-290.

[3] LIU Yuping,SUN Baoguo,XIE Jianchun,et al. Synthesise of Vanillin Propylene Glycol Acetal Catalyzed by NaHSO4[J]. Fine Chem,2004,21](11):831-832,846(in Chinese).

刘玉平,孙宝国,谢建春,等. 硫酸氢钠催化合成香兰素丙二醇缩醛[J]. 精细化工,2004,21](11):831-832,846.

[4] Egi M,Sugiyama K,Saneto M,et al. A Mesoporous-silica-immobilized Oxovanadium Cocatalyst for the Lipase-catalyzed Dynamic Kinetic Resolution of Racemic Alcohols[J]. Angew Chem Int Ed,2013,52]:3654-3658.

[5] Alvarez H M,Barbosa D P,Fricks A T,et al. Production of Piperonal, Vanillin, and p-Anisaldehyde via Solventless Supported Iodobenzene Diacetate Oxidation of Isosafrol, Isoeugenol, and Anethol under Microwave Irradiation[J]. Org Process Res Dev,2006,10]:941-943.

[6] Drago R S,Corden B B,Barnes C W. Novel Cobalt(Ⅱ)-catalyzed Oxidative Cleavage of a Carbon-carbon Double Bond[J]. J Am Chem Soc,1986,108]:2453-2454.

[7] Gusevskaya E V,Menini L,Parreira L A,et al. Oxidation of Isoeugenol to Vanillin by the “H2O2-vanadate-pyrazine-2-carboxylic Acid” Reagent[J]. J Mol Catal A:Chem,2012,363/364]:140-147.

[8] Ligtenbarg A G J,Hage R,Feringa B L. Catalytic Oxidations by Vanadium Complexes[J]. Coord Chem Rev,2003,237]:89-101.

[9] SHI Xiaobo,MO Chunsheng,LI Chungen. Hydroxylation of Benzene into Phenol Catalyzed by Nano-heteropolymolybdovanadoph-osphates[J]. Chinese J Appl Chem,2005,22](1):19-23(in Chinese).

石晓波,莫春生,李春根. 纳米磷钼钒杂多酸盐催化苯羟基化合成苯酚[J]. 应用化学,2005,22](1):19-23.

[10] Xiao Y,Huang H M,Yin D L,et al. Oxidation of Anethole with Hydrogen Peroxide Catalyzed by Oxovanadium Aromatic Carboxylate Complexes[J]. Catal Commun,2008,10]:29-32.

[11] Hallett J P,Welton T. Room-temperature Ionic Liquids:Solvents for Synthesis and Catalysis. 2[J]. Chem Rev,2011,111]:3508-3576.

[12] Chen X W,Li X H,Hu A X,et al. Advances in Chiral Ionic Liquids Derived from Natural Amino Acids[J]. Tetrahedron:Asymmetry,2008,19]:1-14.

[13] Fu Y,Li G B,Liao F H,et al. Two Novel Transition Metal-organic Frameworks Based on 1,3,5-Benzenetricarboxylate Ligand:Syntheses, Structures and Thermal Properties[J]. J Mol Struct,2011,1004]:252-256.

[14] Lane B S,Burgess K. Metal-catalyzed Epoxidations of Alkenes with Hydrogen Peroxide[J]. Chem Rev,2003,103]:2457-2473.

[15] ZHAO Yanqing,WANG Hongyu，GAO Guitian,et al. Synthesis and Electrochemical Properties of Short-chain Hydroxyl Methyl Imidazole Ionic Liquids[J]. Chinese J Appl Chem,2012,29](12):1457-1462(in Chinese).

赵艳青,王宏宇,高桂天,等. 短链羟基甲基咪唑离子液体的合成与电化学性能[J]. 应用化学,2012,29](12):1457-1462.

[16] Mota A,Butenko N,Hallett J P,et al. Application of VⅣO(acac)2 Type Complexes in the Desulfurization of Fuels with Ionic Liquids[J]. Catal Today,2012,196]:119-125.

[17] Olivier-Bourbigou H,Magna L,Morvan D. Ionic Liquids and Catalysis:Recent Progress from Knowledge to Applications[J]. Appl Catal A:Gen,2010,373]:1-56.

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