负载型离子液体催化芳香烯和甲醛的Prins缩合反应
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摘要
采用溶胶凝胶法制备了一系列硅胶负载型离子液体催化剂(IL/sg),并成功应用于甲醛与苯乙烯及其衍生物的Prins反应中.利用红外光谱(FT-IR)、元素分析(EA)和氮气吸附-脱附等对催化剂结构进行了表征.研究表明,磺酸功能化离子液体1-甲基-3-丁磺酸基咪唑硫酸氢盐固载得到的负载型催化剂(Bs MIm HSO4/sg)表现出最佳的催化活性.在催化剂投料量为烯烃的3%,甲醛与烯烃摩尔比为4∶1,80℃下反应8 h,苯乙烯转化率达到了100%,产物选择性为90%.催化剂经简单的过滤分离后重复使用5次,仍保持良好的催化活性.此外,该催化体系具有较好的底物适用性.
A series of silica gel supported ionic liquids catalysts( IL / sg) has been successfully synthesized via solgel method and applied as catalyst for Prins reaction between formaldehyde with styrene and its derivatives. The structure of catalysts is characterized by various techniques including elemental analysis,FT-IR and nitrogen adsorption-desorption. The results show that silica gel supported 1-methyl-3-( 3-sulfobutyl) imidazolium hydrogen sulfate( Bs MIm HSO4/ sg) has the best catalytic activity with a performance of complete conversion of styrene and high selectivity( 90%) of 4-phenyl-1,3-dioxane under conditions of n( catalyst) ∶ n( styrene) = 3%,n( formaldehyde) ∶n( styrene) = 4 ∶ 1,reaction temperature 80 ℃ and reaction time 8 h. The catalyst is able to be conveniently s eparated from the reaction system and maintain good catalytic activity after reused five times. In addition,the catalytic system has excellent substrate applicability.
A series of silica gel supported ionic liquids catalysts( IL / sg) has been successfully synthesized via solgel method and applied as catalyst for Prins reaction between formaldehyde with styrene and its derivatives. The structure of catalysts is characterized by various techniques including elemental analysis,FT-IR and nitrogen adsorption-desorption. The results show that silica gel supported 1-methyl-3-( 3-sulfobutyl) imidazolium hydrogen sulfate( Bs MIm HSO4/ sg) has the best catalytic activity with a performance of complete conversion of styrene and high selectivity( 90%) of 4-phenyl-1,3-dioxane under conditions of n( catalyst) ∶ n( styrene) = 3%,n( formaldehyde) ∶n( styrene) = 4 ∶ 1,reaction temperature 80 ℃ and reaction time 8 h. The catalyst is able to be conveniently s eparated from the reaction system and maintain good catalytic activity after reused five times. In addition,the catalytic system has excellent substrate applicability.
引文
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[16]Lei Min(雷敏),Zhao Yingwei(赵应伟),Wu Li(吴丽),et al.The prins reaction of alkenes with triformol catalyzed by acidic functional ionic liquids(酸功能化离子液体催化三聚甲醛与烯烃的Prins反应)[J].J Mol Catal(China)(分子催化),2013,27(2):107-114.
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[18]Zhang Ai-hua(张爱华),Zhang Yu-jun(张玉军),Li Chang-zhu(李昌珠),et al.Synthesis of biodiesel catalyzed by 1-(4-Sulfonic Acid)butyl-pyridinium hydrosulfate ionic liquid(吡啶丁烷磺酸硫酸氢盐离子液体催化制备生物柴油)[J].Petrochem Technol(China)石油化工,2009,38(4):389-393.
[19]Chiappe C,Rajamani S.Structural effects on the physico-chemical and catalytic properties of acidic ionic l iquids:An overview[J].Eur J Org Chem,2011,(28):5517-5539.
[2]Alarcón E A,Correa L,Montes C,et al.Nopol production over Sn-MCM-41 synthesized by different proceduresSolvent effects[J].Micro Mes Mater,2010,136(1/3):59-67.
[3]Selvaraj M,Choe Y.Well ordered two-dimensional Sn SBA-15 catalysts synthesized with high levels of tetrahedral tin for highly efficient and clean synthesis of nopol[J].Appl Catal,A,2010,373(1/2):186-191.
[4]Amrute A P,Sahoo S,Bordoloi,et al.Mo O3/Si O2:An efficient and selective catalyst for the synthesis 1,3-dioxolane and 1,3-dioxane[J].Catal Commun,2009,10(10):1404-1409.
[5]Zhang W,Leng Y,Huang,J,et al.Heteropolyacid salts of N-methyl-2-pyrrolidonium as highly efficient and reusable catalysts for Prins reactions of styrenes with formalin[J].Green Chem,2011,13(4):832-834.
[6]Marakatti V S,Shanbhag G V,Halgeri A B.Sulfated zirconia;an efficient and reusable acid catalyst for the selective synthesis of 4-phenyl-1,3-dioxane by Prins cyclization of styrene[J].Appl Catal,A,2013,451:71-78.
[7]Wang Y,Wang F,Xu J,et al.Heterogeneous ceria catalyst with water-tolerant Lewis acidic sites for one-pot synthesis of 1,3-diols via Prins condensation and hydrolysis reactions[J].J Amer Chem Soc,2013,135(4):1506-1515.
[8]Costa V.V,Bayahia H,Kozhevnikov I V,et al.Highly active and recyclable metal oxide catalysts for the prins condensation of biorenewable feedstocks[J].Chem Cat Chem,2014,6(7):2134-2139.
[9]More G P,Rane M,Bhat S V.Efficient Prins cyclization in environmentally benign method using ion exchange resin catalyst[J].Green Chem Lett Rev,2012,5(1):13-17.
[10]a.Cole A C,Jensen J L,Ntai I.Novel Brnsted acidic ionic liquids and their use as dual solvent-catalysts[J].J Amer Chem Soc,2002,124(21):5962-5963.b.Zhang Xin(张欣),Yang Cai-ling(杨彩玲),Song Wei-wei(宋伟伟),et al.IL-Based nanoparticles palladium:a highly efficient catalyst for double carbonylation reaction to the preparation ofα-keto amide(离子液体制备纳米钯催化碘代芳烃双羰化反应合成α-酮酰胺)[J].J Mol Catal(China)(分子催化),2014,28(4):312-316.c.He Zhi-cheng(何志成),Wu Zhi-min(吴志民),Li Yong-fei(李勇飞),et al.Synthesis of bispheol F catalyzed by sulfonic acid-functionalized dicationic imidazolium ionic liquids(磺酸功能化双核离子液体催化合成双酚F)[J].J Mol Catal(China)(分子催化),2014,28(6):535-543.
[11]a.Wang A,Zheng X,Yang G,et al.Brnsted acid ionic liquids catalyzed Friedel-Crafts Alkylations of electron-rich arenes with aldehydes[J].Appl Catal,A,2014,482:198-204.b.Ren Yun-lai(任运来),Wang Pei(王胚),Tian Xinzhe(田欣哲),et al.Ionic liquid/H2SO4catalyzed aerobic iodination of alkoxyl-substituted benzenes and naphthalines(离子液体/H2SO4催化烷氧基取代苯和萘的需氧碘化)[J].J Mol Catal(China)(分子催化),2015,29(6):505-512.c.Lu Chao(鲁超),Su Er-zheng(苏二正),Wei Dongzhi(魏东芝),et al.The applications of deep eutectic solvents in biocatalysis(深共熔溶剂的生物催化应用)[J].J Mol Catal(China)(分子催化),2015,29(4):390-401.
[12]Wang H,Tan B,Zhang S,et al.Anion-based p H responsive ionic liquids:design,synthesis,and reversible self-assembling structural changes in aqueous solution[J].Langmuir,2014,30(14):3971-3978.
[13]Wang W,Shao L,He M,et al.Brnsted acidic ionic liquids as novel catalysts for Prins reaction[J].Catal Commun,2008,9(3):337-341.
[14]Gu Y,Ogawa C,Kobayashi S.Novel hydrophobic Brnsted acidic ionic-liquids as efficient and reusable c atalysts for organic reactions in water[J].Chem Lett,2006,35(10):1176-1177.
[15]Kalkhambkar R G,Jeong Y T.Highly efficient synthesis of 1,3-dioxanes via prins reaction in Brnsted-acidic imidazolium ionic liquid[J].Synth Commun,2014,44(6):762-771.
[16]Lei Min(雷敏),Zhao Yingwei(赵应伟),Wu Li(吴丽),et al.The prins reaction of alkenes with triformol catalyzed by acidic functional ionic liquids(酸功能化离子液体催化三聚甲醛与烯烃的Prins反应)[J].J Mol Catal(China)(分子催化),2013,27(2):107-114.
[17]Hajipour A R,Rajaei A,Ruoho A E.A mild and efficient method for preparation of azides from alcohols using acidic ionic liquid[H-NMP]HSO4[J].Tetra Lett,2009,50(6):708-711.
[18]Zhang Ai-hua(张爱华),Zhang Yu-jun(张玉军),Li Chang-zhu(李昌珠),et al.Synthesis of biodiesel catalyzed by 1-(4-Sulfonic Acid)butyl-pyridinium hydrosulfate ionic liquid(吡啶丁烷磺酸硫酸氢盐离子液体催化制备生物柴油)[J].Petrochem Technol(China)石油化工,2009,38(4):389-393.
[19]Chiappe C,Rajamani S.Structural effects on the physico-chemical and catalytic properties of acidic ionic l iquids:An overview[J].Eur J Org Chem,2011,(28):5517-5539.