Keggin型钨锗酸联咪唑盐催化合成环己酮乙二醇缩酮

doi:10.3724/SP.J.1095.2014.30653

摘要/Abstract

摘要： 设计合成了Keggin型钨锗酸联咪唑盐(H4biim)[H2GeW12O40]·18H2O(1b，H2biim=2,2′-联咪唑), 并将其用于催化合成环己酮乙二醇缩酮反应。通过X射线单晶衍射、红外光谱(FT-IR)、紫外光谱(UV)、热重-差热(TG-DTA)、粉末衍射(XRD)等技术手段对催化剂1b进行了表征。较系统地研究了反应物料比、催化剂用量、反应时间等因素对催化反应的影响。在n(环己酮)∶n(乙二醇)=1∶1.4，n(1b，以W计)∶n(环己酮)=1∶260,反应2 h的优化反应条件下，目标化合物产率达90%，催化剂可循环使用，表现出良好的催化稳定性。

关键词: Keggin结构, 钨锗酸盐, 联咪唑, 羰基保护, 催化

Abstract: A Keggin-type biimidazole tungstogermanate(H4biim)[H2GeW12O40]·18H2O(1b, H2biim=2,2′-biimidazole), as a catalyst for the synthesis of cyclohexanone ethylene ketal, was designed and synthesized. It was characterized by single crystal X-ray diffraction analysis, infrared spectroscopy(FT-IR), ultraviolet spectroscopy(UV), themogravimetrydifferential thermal analysis(TG-DTA) and X-ray powder diffraction(XRD). Factors, such as the molar ratio of cyclohexanone to ethylene glycol, catalyst loading and reaction time, on the yield were investigated. The experimental results show that the product yield reaches 90% under the optimal conditions:n(cyclohexanone)∶n(1,2-ethanediol)=1∶1.4, n(1b, based on W)∶n(cyclohexanone)=1∶260, reaction time is 2 h. The catalyst can be reused and has good stability in the catalytic reaction.

Key words: Keggin-type Structure, tungstogermanate, biimidazole, carbonyl-protecting reaction, catalysis

中图分类号:

O614.6

杨柳, 卢明达, 张澜萃, 张柏, 孙航, 朱再明. Keggin型钨锗酸联咪唑盐催化合成环己酮乙二醇缩酮[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30653.

YANG Liu, LU Mingda, ZHANG Lancui*, ZHANG Bai, SUN Hang, ZHU Zaiming*. Synthesis of Cyclohexanone Ethylene Ketal Catalyzed by Keggin Type Biimidazole Tungstogermanate[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30653.

参考文献

[1] WEN Ruiming,YOU Peiqing,YU Shanxin. Progress of Synthesis of Cyclohexanone Ethylene Ketal Catalyzed by Solid Acids[J]. Chem Ind Eng Prog,2007,26(11):1587-1595(in Chinese).

文瑞明,游沛清,俞善信. 合成环己酮乙二醇缩酮的催化剂研究进展[J]. 化工进展,2007,26(11):1587-1595.

[2] ZHANG Heng,WANG Min,ZHU Wancheng,et al. Preparation of Kaolinite Supported SO2-4/ZrO2-TiO2 Catalyst and Its Application in Cyclohexanone Ethylene Ketal Synthesis[J]. Chinese J Appl Chem,2011,28(5):608-610(in Chinese).

张恒，王敏，朱万诚，等. 高岭土负载SO2-4/ZrO2-TiO2催化剂的制备及其在缩酮合成中的应用[J]. 应用化学,2011,28(5):608-610.

[3] GONG Wenpeng,YANG Shuijin. Progress of Research on Solid Acid Catalysts for Synthesis of Cyclohexanone Ethylene Ketal[J]. Adv Fine Petrochem,2013,14(2):29-33(in Chinese).

龚文朋,杨水金. 固体酸催化合成环己酮乙二醇缩酮研究进展[J]. 精细石油化工进展,2013,14(2):29-33.

[4] Tamiolakis I,Lykakis I N,Katsoulidis A P,et al. Ordered Mesoporous Cr2O3 Frameworks Incorporating Keggin-type 12-Phosphotungstic Acids as Efficient Catalysts for Oxidation of Benzyl Alcohols[J]. J Mater Chem,2012,22(14):6919-6927.

[5] Linguito S L,Zhang X,Padmanabhan M,et al. New Polyoxomolybdate Compounds Synthesized in Situ Using Ionic Liquid 1-Butyl-3-methyl-imidazolium Tetrafluoroborate as Green Solvent[J]. New J Chem,2013,37(9):2894-2901.

[6] Leng Y,Wang J,Zhu D R,et al. Polyoxometalate-based Amino-functionalized Ionic Solid Catalysts Lead to Highly Efficient Heterogeneous Epoxidation of Alkenes with H2O2[J]. Green Chem,2011,13(7):1636-1639.

[7] Yang H,Li J,Wang L Y,et al. Exceptional Activity for Direct Synthesis of Phenol from Benzene over PMoV@MOF with O2[J]. Catal Commun,2013,35:101-104.

[8] Yang H,Wu Q,Li J,et al. Direct Synthesis of Phenol from Benzene Catalyzed by Multi-V-POMs Complex[J]. Appl Catal A:Gen,2013,457:21-25.

[9] Wang P C,Yao K,Lu M. Preparation of Heteropoly Acid Based Amphiphilic Salts Supported by Nano Oxides and Their Catalytic Performance in the Nitration of Aromatics[J]. RSC Adv,2013,3(7):2197-2202.

[10] Yang L M,Yin Z K,Wu L Q. H4SiW12O40:An Efficient Catalyst for the Synthesis of New Spiro-[dibenzo[a,i]xanthene-14,3′-indoline]-2′,8,13-triones[J]. Chinese Chem Lett,2012,23(3):265-268.

[11] Wu S S,Liu P,Leng Y,et al. Heteropolyacids Anchored on Amino-Functionalized MCM-41 via Condensation as Reusable Catalysts for Esterification[J]. Catal Lett,2009,132(3-4):500-505.

[12] Rahimizadeh M,Bazazan T,Shiri A,et al. Preyssler-type Heteropoly Acid:A New, Mild and Efficient Catalyst for Protection of Carbonyl Compounds[J]. Chinese Chem Lett,2011,22(4):435-438.

[13] XU Zhaohui,LIAO Weilin,LUO Nianhua,et al. Sythesis of Cyclohexanone Ethylene Ketal over Wells-Dawson Type Tungstenvanadophoric Heteropolyacid[J]. Chem Res Appl,2006,18(2):199-201(in Chinese).

许招会,廖维林,罗年华,等. Dawson型磷钨钒杂多酸催化合成环己酮乙二醇缩酮[J]. 化学研究与应用,2006,18(2):199-201.

[14] FAN Naili,LIAO Weilin,WANG Shen,et al. Synthesis of Cyclohexanone Ethylene Ketal over LaPWl2O40 Catalyst[J]. Ind Catal,2008,16(12):72-75 (in Chinese).

范乃立,廖维林,王甡,等. 磷钨酸镧催化合成环己酮乙二醇缩酮[J]. 工业催化,2008,16(12):72-75.

[15] XU Zhaohui,CHEN Dekai,HUANG Yixiang,et al. Green Synthesis of Cyclohexanone Ethylene Ketal over LaSiW12O40 Catalyst[J]. Ind Catal,2005,13(10):40-42(in Chinese).

许招会,陈德锴,黄宜祥,等. 硅钨酸镧绿色合成环己酮乙二醇缩酮[J]. 工业催化,2005,13(10):40-42.

[16] WANG Enbo,HU Changwen,XU Lin. Introduction of Polyacid Chemistry[M]. 1st Edition. Beijing:Chemical Industry Press,1998:171-173(in Chinese).

王恩波,胡长文,许林. 多酸化学导论[M]. 第1版. 北京：化学工业出版社,1998:171-173.

[17] Yang C Y,Zhang L C,Wang Z J,et al. Three New Extended Preyssler-type Polyoxometalates Modified by Transition Metal-2,2′-biimidazole Complexes[J]. J Solid State Chem,2012,194:270-276.

[18] Jin H J,Zhou B B,Yu Y,et al. Inorganic-organic Hybrids Constructed from Heteropolymolybdate Anions and Copper-organic Fragments:Syntheses, Structures and Properties[J]. Cryst Eng Comm,2011,13(2):585-590.

[19] Wang J L,Zhang L C,Li X H,et al. Three 2,2′-Biimidazole Transition Metal Complex-supported Octamolybdates Derived from Hexamolybdochromate[J]. Trans Met Chem,2012,37(3):303-307.

[20] Wang Y,Zhang L C,Zhu Z M,et al. Assembly of Four Copper(Ⅱ)-2,2′-biimidazole Complex-supported Strandberg-type Phosphomolybdates[J]. Trans Met Chem,2011,36(3):261-267.

[21] Herve G,Teze A. Study of Alpha- and Beta-enneatungstosilicates and Germanates[J]. Inorg Chem,1977,16(8):2115-2117.

[22] Sheldrick G M. SHELXL97,Program for Crystal Structure Refinement [CP]. University of Gttingen,Gttingen,Germany,1997.

[23] Lu Y,Wang E B,Guo Y Q,et al. Hydrothermal Synthesis and Crystal Structure of a Hybrid Material Based on [Cu4(bpy)4(H2O)2(PO4)2]2+ and an α-Keggin Polyoxoanion[J]. J Mol Struct,2005,737(2/3):183-187.

[24] Meng C L,Zhang P P,Peng J,et al. Keggin-Type Polyoxometalate Cluster Functionalized with Dinuclear M-H2biim(M=Cu,Ag) Metal-Organic Segments[J]. J Clust Sci,2012,23(2):567-576.

[25] Zhang C H,Chen Y G,Liu S X. Supramolecular Compounds Constructed by Main Group Metals, Polyoxotungstates and Polyaminepolycarboxylate[J]. Solid State Sci,2013,20:80-85.

[26] Thorp H H. Bond Valence Sum Analysis of Metal-ligand Bond Lengths in Metalloenzymes and Model Complexes[J]. Inorg Chem,1992,31(9):1585-1588.

[27] Hu Y Y,Xiao L N,Wang Y,et al. New Compounds Based on Polyoxometalates and Transition Metal Complexes with a Lower Positive Charge[J]. Polyhedron,2013,56:152-159.

[28] ZHU Zaiming,YOU Wansheng,SUN Zhen′gang,et al. Synthesis, Structure and Properties of K3[Cr3O(OOCH)6(H2O)3][α-GeWl2O40]·17H2O[J]. J Mol Sci,2005,21(1):47-53 (in Chinese).

朱再明,由万胜,孙振刚,等. K3[Cr3O(OOCH)6(H2O)3][α-GeWl2O40]·17H2O的合成、结构及特性研究[J]. 分子科学学报,2005,21(1):47-53.

[29] Tao D J,Li Z M,Cheng Z,et al. Kinetics Study of the Ketalization Reaction of Cyclohexanone with Glycol Using Brnsted Acidic Ionic Liquids as Catalysts[J]. Ind Eng Chem Res,2012,51(9):16263-16269.

[30] Liu J H,Wei X F,Yu Y L,et al. Uniform Core-shell Titanium Phosphate Nanospheres with Orderly Open Nanopores:A Highly Active Brnsted Acid Catalyst[J]. Chem Commun,2010,46(10):1670-1672.