温控两相酸性聚合型离子液体催化胺醛缩合反应

doi:10.11944/j.issn.1000-0518.2017.04.160261

摘要/Abstract

摘要：

为降低催化剂流失率,以聚乙二醇为主链、双键取代咪唑型离子液体为交联剂,采用自由基聚合方式设计合成出酸性聚合型离子液体。该离子液体可与甲苯形成优良的温控两相体系,并用于苯胺和苯甲醛的缩合反应。结果表明,聚合离子液体具有催化活性高、流失量小、回收方便的优点。产物N-亚苄基苯胺收率93.4%,离子液体平均单次流失率约2.5%。底物拓展试验表明,该温控体系对含不同取代基的芳胺和芳醛缩合反应具有良好的普适性,产物收率57.2%~82.9%。

关键词: 温控两相, 离子液体, 聚乙二醇, 聚合, 催化

Abstract:

Acidic polymeric ionic liquid was synthesized with polyethylene glycol as the main chain and imidazole-based ionic liquid as crosslinking agent through the free radical polymerization to reduce the loss rate of catalyst. The thermoregulated biphasic system comprised of ionic liquid and toluene was used for the condensation reaction of aniline and benzaldehyde. The catalytic results show that the catalyst has advantages of high catalytic activity, small loss and easy recycling. The yield of N-benzalaniline is 93.4%, and the average loss rate of ionic liquid is about 2.5%. Further tests show that the system has good universality for the various substrates, and the yield of the products is 57.2%~82.9%.

Key words: thermoregulated biphase, ionic liquid, polyethylene glycol, polymerization, catalysis

毕波, 开旺, 任丽萍, 钱华. 温控两相酸性聚合型离子液体催化胺醛缩合反应[J]. 应用化学, 2017, 34(4): 394-401.

BI Bo, KAI Wang, REN Liping, QIAN Hua. Thermoregulated Biphasic Acidic Polymeric Ionic Liquid Catalyzed Amine Aldehyde Condensation Reaction[J]. Chinese Journal of Applied Chemistry, 2017, 34(4): 394-401.

参考文献

[1]	JIN Zilin,LIU Ning,LIU Chun.Thermoregulated Liquid/Liquid Biphasic Catalysis[J]. Prog Chem,2010,22(7):1295-1308(in Chinese). 金子林,刘宁,刘春. 温控液/液两相催化进展[J]. 化学进展,2010,22(7):1295-1308.
[2]	YANG Yuchuan,WEI Li,JIN Zilin.New Progress in Liquid/Liquid Biphasic Catalysis-Thermoregulated Non-aqueous Liquid/Liquid Biphasic Catalysis[J]. Chinese J Org Chem,2004,24(6):579-584(in Chinese). 杨玉川,魏莉,金子林. 液/液两相催化新进展—温控非水液/液两相催化[J]. 有机化学,2004,24(6):579-584.
[3]	Zhu J,Wang P C,Lu M.Synthesis of Novel Magnetic Silica Supported Hybrid Ionic Liquid Combining TEMPO and Polyoxometalate and Its Application for Selective Oxidation of Alcohols[J]. RSC Adv,2012,2(2):8265-8268.
[4]	Feng G L,Wang Y H,Jiang J Y,et al.Using Thermoregulated PEG Biphasic System to Effect the Hydroformylation of p-Isobutylsrene Catalyzed by Rh/OPGPP Complex[J]. J Mol Catal A Chem,2006,248(1):159-162.
[5]	Wang Y H,Jiang J Y,Jin Z L.Thermoregulated Liquid/Liquid Biphasic Catalysis and Its Application[J]. Catal Surveys Asia,2004,8(2):119-126.
[6]	LIU Xiaobing,ZHONG Luping,HU Yulin.Study on Dehydration of Fructose Catalyzed by Ionic Liquid in Thermoregulated Biphasic System[J]. Guangdong Chem Ind,2015,42(11):42-43(in Chinese). 刘小兵,钟路平,胡玉林. 温控两相体系中离子液体催化果糖脱水的研究[J]. 广东化工,2015,42(11):42-43.
[7]	HU Yulin,LU Ming,FANG Dong.Study on the Synthesis of Tetrahydro-β-carboline Derivatives in PEG1000-DAIL/Toluene Temperature-dependent Biphasic System[J]. J Yancheng Inst Technol(Nat Sci Ed),2013,26(3):14-19(in Chinese). 胡玉林,陆明,方东. PEG1000-DIL/甲苯温控两相体系催化四氢-β-咔啉类化合物的合成研究[J]. 盐城工学院学报:自然科学版,2013,26(3):14-19.
[8]	Nguyen M D,Nguyen L V,Jeon E H,et al.Fe-containing Ionic Liquids as Catalysts for the Dimerization of Bicyclo[2.2.1]hepta-2,5-diene[J]. J Catal,2008,258(1):5-13.
[9]	Bica K,Gaertner P.Metal-Containing Ionic Liquids as Efficient Catalysts for Hydroxymethylation in Water[J]. Eur J Org Chem,2008,2008(20):3453-3456.
[10]	Huddleston J G,Rogers R D.Room Temperature Ionic Liquids as Novel Media for ‘clean’ Liquid liquid Extraction[J]. Chem Commun,1998,16(16):1765-1766.
[11]	HU Yulin.Study on the Unit Reactions of Organic Synthesis in Ionic Liquid Biphasic Systems[D]. Nanjing:Nanjing University of Science and Technology,2012:33-53(in Chinese). 胡玉林. 离子液体两相催化体系在有机单元反应中的研究[D]. 南京:南京理工大学,2012 :33-53.
[12]	ZHI Huizhen,LUO Jun,LV Chunxu.Esterification of Aromatic Acids and Alcohols in Acidic PEG Thermoregulated Ionic Liquids[J]. Chem J Chinese Univ,2008,29(4):772-774(in Chinese). 职慧珍,罗军,吕春绪. PEG型酸性温控离子液体中芳香酸和醇的酯化反应[J]. 高等学校化学学报,2008,29(4):772-774.
[13]	ZHI Huizhen,LUO Jun,LV Chunxu.Acetalization of Aromaldehyde and Ethyleneglycol in Novel PEG Thermoregulated Ionic Liquids[J]. Chem J Chinese Univ,2008,29(10):2007-2010(in Chinese). 职慧珍,罗军,吕春绪. 新型PEG型双子温控离子液体中的缩醛反应[J]. 高等学校化学学报,2008,29(10):2007-2010.
[14]	ZHI Huizhen,WANG Yinglei,ZHANG Qiang.Reduction of Nitroarenes in PEG1000-DIL/Toluene Thermoregulated Biphasic System[J]. Chem J Chinese Univ,2013,34(3):573-578(in Chinese). 职慧珍,王英磊,张强. PEG1000-DIL/甲苯温控两相体系中硝基芳烃的还原反应[J]. 高等学校化学学报,2013,34(3):573-578.
[15]	XING Tantan.Synthesis of a Shuangyang Ionic Ionic Liquid Alkaline with Thermoregulated Biphasic and Its Application in Organic Reaction[D]. Nanjing:Nanjing University Science Technology,2011:33-43(in Chinese). 邢昙昙. 具有温控两相性质的双阳离子型碱性离子液体的合成及其在有机反应中的应用[D]. 南京:南京理工大学,2011:33-43.
[16]	Huddlelestn J G.Characterization and Comparison of Hydrophobic Room Temperature Ionic Liqids Incorporation the Imidazolium Cation[J]. Green Chem,2001,3(4):156-164.
[17]	Davis J H.Novel Organic Ionic Liquids(OILS) Incorporating Cations Derived from the Antifungal Drug Miconazole[J]. Tetrahedron Lett,1998,39(49):8955-8958.
[18]	LI Long,MA Cha,YUAN Xubo,et al.Synthesis and Application of Dendrimers in Oilfield Chemistry[J]. Mod Chem Ind,2012,32(6):16-21(in Chinese). 李龙,马茶,苑旭波,等. 树枝状聚合物的合成及其在油田化学中的应用[J]. 现代化工,2012,32(6):16-21.
[19]	Floudas G,Papadopoulos P,Klok H A,et al.Hierarchical Self-assembly of Poly(γ-benzyl-L-glutamate)-poly(ethylene glycol)-poly(γ-benzyl-L-glutamate) rod-coil-rod Triblock Copolymers[J]. Macromolecules,2003,36(11):3673-3683.
[20]	Gibson H W,Yamaguchi N,Jones J W.Supramolecular Pseudorotaxane Polymers From Complementary Pairs of Homoditopic Molecules[J]. J Am Chem Soc,2003,125(12):3522-3533.
[21]	Pourjzvzdi A.Multi-Layer Functionalized Poly(Ionic Liquid) Coated Magnetic Nanoparticles:Highly Recoverable and Magnetically Separable Brønsted Acid Catalyst[J]. ACS Catal,2012,2(6):1259-1266.
[22]	Yu F L,Wang Y Y,Liu C Y,et al.Oxidative Desulfurization of Fuels Catalyzed by Ammonium Oxidative-thermoregulated Bifunctional Ionic Liquids[J]. Chem Eng J,2014,255(7):372-376.
[23]	Nakashima T,Kimizuka N.Inerfacial Synthesis of Hollow TiO2 Microspheres in Ionic Liquids[J]. J Am Chem Soc,2003,125(21):6386-6387.
[24]	GAO Hongbin.Organic Chemistry[M]. 4th Ed. Beijing:Higher Edution Press,2010:395-397(in Chinese). 高鸿宾. 有机化学[M]. 第4版. 北京:高等教育出版社,2010:395-397.