硅胶固定功能化离子液体的制备及其在HMF合成中的应用

通过氯丙基三甲氧基硅烷将磺基功能化离子液体--N-磺丙基咪唑盐化学键联到微球硅胶上,制得微球硅胶固定化离子液体（IL3）。用FTIR、TG、13C-NMR、SEM、BET及酸度测定等方法对IL3进行了表征,并考察其在果糖脱水合成5-羟甲基糠醛（HMF）过程中的催化性能。研究结果表明：氯丙基三甲氧基硅烷可以将磺基功能化咪唑型离子液体化学键联到微球硅胶上。微球硅胶固定化磺基咪唑离子液体能有效催化果糖脱水生成HMF。在45.4-IL3催化下、乙二醇甲醚(EGME)溶剂中、115℃反应5小时, HMF收率可达82.1％。使用后的催化剂可以方便地循环使用。但随次数增加,HMF收率明显下降。45.4-IL3催化剂循环使用四次后,HMF的收率下降为53.0%。     

果糖在酸性离子液体中脱水制备5-羟甲基糠醛

制备了多种离子液体,并将其作为催化剂和溶剂催化果糖脱水制备5-羟甲基糠醛（HMF）。 制备的酸性离子液体包括磺酸基功能化酸性离子液体、咪唑类酸性离子液体和吡啶类酸性离子液体。 利用核磁共振仪和红外光谱仪对离子液体的结构进行表征。 利用紫外可见光分光光度计结合Hammett指示剂计算Hammett酸度函数,比较了酸强度的大小对反应的影响。 结果表明,离子液体的酸强度对反应有较大影响,在无其它催化剂和溶剂的情况下,离子液体具有较高的催化活性,通过使用1-丁基-3-甲基咪唑氯盐(BmimCl)作为催化剂,当反应温度为120 ℃,反应进行到4 h时,HMF收率可以达到74.97%。     

离子液体中磺化无定形炭催化菊糖制备5-羟甲基糠醛

研究了以1-丁基-3-甲基咪唑氯盐([Bmim]Cl)离子液体作溶剂,磺化无定形炭为催化剂催化菊糖脱水制5-羟甲基糠醛(HMF)的反应.考察了溶剂、水量、反应温度、反应时间和催化剂用量对HMF收率的影响.实验结果表明,反应温度为100°C,反应时间60min,R=5(R为水的物质的量与菊糖中所含果糖单位的物质的量的比值),m(催化剂):m(菊糖)=1:3时,HMF的收率可达50%.     

吗啡啉功能化酸性离子液体的合成、表征及其催化酯化性能

制备和表征了三种新型质子酸离子液体: 吗啡啉硫酸氢盐([Hnhm]HSO4)、4-甲基吗啡啉硫酸氢盐 ([Hnmm]HSO4)和SO3H-功能化的4-(3-磺丙基)吗啡啉硫酸氢盐([C3SO3Hnhm]HSO4). 以氯乙酸(CAA)和乙醇合成氯乙酸乙酯的酯化反应考察了它们的酸性和催化活性, 并与1-(3-磺酸基)丙基-3-甲基咪唑硫酸氢盐、1-(3-磺丙基)吡啶硫酸氢盐、1-(3-磺丙基)-2-吡咯烷酮硫酸氢盐等三种具有不同氮杂环的SO3H-功能化酸性离子液体以及浓硫酸相对照. 结果表明, 上述SO3H-功能化离子液体对酯化反应的催化性能比非SO3H-功能化的[Hnhm]HSO4和[Hnmm]HSO4都高, 等同甚至优于浓硫酸. 当反应条件为: n(EtOH)∶n(CAA)∶n([C3SO3Hnhm]HSO4)＝1.3∶1∶0.2, 反应温度80 ℃, 反应时间3 h, 酯收率可达93.4%. 而且离子液体经真空干燥重复使用9次, 催化活性仍无明显下降. 以[C3SO3Hnhm]HSO4催化乙酸和不同醇的酯化反应获得较高的酯收率和选择性, 离子液体跟酯产物均能自动分相. 还考察了SO3H-功能化酸性离子液体对奥氏体316不锈钢的腐蚀性. 尽管SO3H-功能化离子液体与硫酸的酸性相近, 但对钢试样的腐蚀率不到硫酸的1/3.     

己内酰胺功能化离子液体的合成及其催化酯化性能的研究

以价格低廉的己内酰胺为原料,制备和表征了4种己内酰胺功能化离子液体:1-(3-磺丙基)己内酰胺硫酸氢盐([C3SO3HCP]HSO4)、1-(3-磺丙基)己内酰胺对甲苯磺酸盐([C3SO3HCP]PTSA)、1-(3-磺丙基)己内酰胺磷酸氢盐([C3SO3HCP]H2PO4)、1-(3-磺丙基)己内酰胺四氟硼酸盐([C3SO3HCP]BF4).以乙酸和乙醇的酯化反应考察4种酸性离子液体的催化活性,并与3种具有不同氮杂环的SO3H-功能化离子液体和浓硫酸相对照.结果表明:当n(C2H5OH)∶n(CH3COOH)=1∶1.5,催化剂[C3SO3HCP]HSO4用量为酸醇总质量的5%,反应温度80℃,反应时间6 h,酯收率可达93.8%,离子液体经真空干燥重复使用10次后,仍具有较高的催化活性,而且对奥氏体316 L不锈钢试样的腐蚀率不到浓硫酸的1/6.还考察了以[C3SO3HCP]HSO4为催化剂催化合成系列乙酯也获得了较高的酯收率,且离子液体均能与酯产物自动分相.与传统硫酸催化酯化相比,此类离子液体催化酯化具有生产成本低、过程清洁、腐蚀率低、使用周期长等优点,具有替代传统浓硫酸催化醇酸酯化反应的潜力.     

具有表面活性的功能化离子液体N-(三甲氧硅丙基)-N-甲基-2-吡咯烷酮盐酸盐的合成与表征

以N-甲基-2-吡咯烷酮和3-氯丙基三甲氧基硅烷单体为原料,利用SN2亲核取代反应合成具有一定表面活性的功能化离子液体N-(三甲氧硅丙基)-N-甲基-2-吡咯烷酮盐酸盐.通过元素分析、红外光谱和核磁共振对功能化离子液体进行表征,并测定了其表面张力和导电率.结果表明,合成的产物结构与其理论结构基本一致,具有较宽的液体温度范围和较低的表面张力,并具有较高的电导率,随着温度的升高,电导率逐渐增高.     

十八烷基离子液体杂化固相微萃取整体柱用于检测咖啡中的多环芳烃

以自制的1-十八烷基-3-(γ-三乙氧基硅基丙基)咪唑溴盐离子液体(C18IL)、二苯基二甲氧基硅烷(DDS)和四乙氧基硅烷(TEOS)为功能单体,采用溶胶-凝胶法制备了烷基咪唑基离子液体管内固相微萃取整体柱(C18IL in-tube SPME).以多环芳烃为分析对象,考察了C_(18)IL含量对C_(18)IL in-tube SPME萃取性能的影响,并对萃取条件进行了优化.建立了基于C_(18)IL in-tube SPME-气相色谱(GC-FID)的分析方法,用于检测萘、芴、菲、荧蒽和芘5种多环芳烃.该方法的检出限(S/N=3)为0.007~0.072μg/L,定量限(S/N=10)为0.023~0.24μg/L,日内和日间精密度(RSD)除菲类多环芳烃外均小于10%.将该方法用于检测咖啡中5种多环芳烃,3个不同浓度下的加标回收率为85.79%~103.42%.     

磺酸功能化双核离子液体催化合成双酚F

合成并表征了4种具有Brnsted酸性的磺酸功能化咪唑类离子液体催化剂,考察了其在催化苯酚、甲醛合成双酚F反应中的催化活性.结果表明磺酸功能化双核离子液体双-(3-磺酸丙基-1-咪唑)亚丁基硫酸氢盐([DPSIM][HSO4]2)不仅催化活性最佳,还提高了4,4’-双酚F异构体的含量.以[DPSIM][HSO4]2为催化剂,在苯酚与甲醛摩尔比30∶1、离子液体催化剂质量浓度6.8%、反应温度90℃、反应时间60 min的优化条件下,双酚F收率可达94.1%,同时提出了其催化合成双酚F的反应机理.该离子液体催化剂腐蚀性低,易分离回收,在重复使用6次后,双酚F收率仍在70%以上.     

咪唑修饰硅胶配位固载锰(Ⅲ)卟啉对环己烷空气氧化的催化作用

应用3-氯丙基三甲氧基硅烷和咪唑成功地对硅胶表面进行了修饰,并通过咪唑基纵轴配位方式固载了四苯基锰(Ⅲ)卟啉.在无任何外加溶剂及共还原剂的条件下,应用此高分子金属卟啉作为催化剂,选择性地催化空气氧化环己烷为环己酮和环己醇.研究结果表明,与未固载金属卟啉相比,固载金属卟啉具有更高的催化活性和催化选择性,反应具有更高的酮醇比,催化剂的稳定性有了较大的提高,便于回收和重复使用.另外还探讨了载体在此催化体系中对催化性能的影响.     

吉非替尼的合成新工艺研究

以6-羟基-7-甲氧基喹唑啉-4-酮(1)为起始原料,在离子液体催化下与N-(3-氯丙基)吗啉(2)醚化,然后经氯代再与3-氯-4-氟苯胺进行亲核取代反应,得到目标产物吉非替尼,三步反应总收率为68.7%。通过改变反应物配比、离子液体用量和反应温度,得到了关键中间体3的优化制备工艺条件:n(1)∶n(2)=1.0∶1.2;离子液体四氟硼酸1-甲基-4-丁基咪唑鎓用量为原料1的质量的5%;95℃下反应5h。在此条件下,醚化收率约93.6%。该路线具有反应条件温和、分离简单、路线短和总收率较高的特点,为吉非替尼的工业化生产提供了实验依据。     

Cellulose sulfuric acid as a bio-supported and recyclable solid acid catalyst for the synthesis of 5-hydroxymethylfurfural and 5-ethoxymethylfurfural from fructose

In this study, we have developed a new and green method for the synthesis of 5-hydroxymethylfurfural (HMF) and 5-ethoxymethylfurfural (EMF) from fructose using cellulose sulfuric acid as catalyst. Firstly, HMF was synthesized from fructose, and a high yield of 93.6 % was obtained in DMSO for 45 min in the presence of cellulose sulfuric acid. Cellulose sulfuric acid also showed high catalytic activity for the synthesis of EMF. EMF was obtained in a high yield of 84.4 % by the etherification of HMF under the optimal reaction conditions. More importantly, a high EMF yield of 72.5 % was also obtained from fructose through one-pot reaction strategy, which integrated the dehydration of fructose into HMF and the followed etherification of HMF into EMF. The reaction work-up was very simple and the catalyst could be reused several times without the loss of its catalytic activity.     

Metal-free dehydration of glucose to 5-(hydroxymethyl)furfural in ionic liquids with boric acid as a promoter

The dehydration of glucose and other hexose carbohydrates to 5-(hydroxymethyl)furfural (HMF) was investigated in imidazolium-based ionic liquids with boric acid as a promoter. A yield of up to 42% from glucose and as much as 66% from sucrose was obtained. The yield of HMF decreased as the concentration of boric acid exceeded one equivalent, most likely as a consequence of stronger fructose-borate chelate complexes being formed. Computational modeling with DFT calculations confirmed that the formation of 1:1 glucose-borate complexes facilitated the conversion pathway from glucose to fructose. Deuterium-labeling studies elucidated that the isomerization proceeded via an ene-diol mechanism, which is different to that of the enzyme-catalyzed isomerization of glucose to fructose. The introduced non-metal system containing boric acid provides a new direction in the search for catalyst systems allowing efficient HMF formation from biorenewable sources.     

果糖催化合成5-羟甲基糠醛研究的新进展

5-羟甲基糠醛(HMF)是一种具有重要应用价值的原材料和中间体,以果糖脱水合成HMF具有实现生物质转化利用的重大意义。本文综述了近三年来果糖制备HMF过程的两大关键因素:催化剂和反应介质的重要进展。固体酸(特别是杂多酸及其盐)、离子液体(ILs)中添加卤化物或ILs作为催化剂是近几年来研究的热点,固体酸的优点是可多次重复使用且易于分离,而ILs中果糖的降解条件较温和,副反应较少。目前,用于果糖转化HMF的反应溶剂优、缺点并存。最后对该反应存在的问题和今后的研究进行了总结和展望。     

磺酸官能化的磁性核壳结构的纳米材料用于果糖脱水制备5-羟甲基糠醛(英)

通过反相微乳液法制备了以Fe₃O₄为核,磺酸官能化的硅基材料为壳层的磁性酸性催化剂.首先制备纳米Fe₃O₄磁核,然后涂层包覆苯基修饰的纳米级硅层,最后进行苯基磺化修饰,制得固体酸催化剂Fe₃O₄@Si/Ph-SO₃H.在果糖脱水制备5-羟甲基糠醛反应中,该催化剂表现出较好的催化活性,优于传统催化剂A-15,且与均相无机酸催化活性相当.当采用二甲基亚砜作溶剂,在110℃下反应3 h,果糖转化率达到99%,5-羟甲基糠醛收率为82%.另外,该催化剂经磁法回收后可多次重复使用.     

Zirconyl schiff base complex-functionalized MCM-41 catalyzes dehydration of fructose into 5-hydroxymethylfurfural in organic solvents

A heterogeneous catalyst was prepared by immobilizing Zirconyl Schiff base complex on the modified MCM-41 and used in the conversion of fructose to HMF. A higher HMF yield was obtained when fructose as raw material under optimal reaction conditions.     

Production of 5‐Hydroxymethylfurfural from Fructose in Ionic Liquid Efficiently Catalyzed by Cr(III)‐Al2O3 Catalyst

A series of metal‐Al₂O₃ catalysts were prepared simply by the conventional impregnation with Al₂O₃ and metal chlorides, which were applied to the dehydration of fructose to 5‐hydroxymethylfurfural (HMF). An agreeable HMF yield of 93.1% was achieved from fructose at mild conditions (100°C and 40 min) when employing Cr(III)‐Al₂O₃ as catalyst in 1‐butyl‐3‐methylimidazolium chloride ([Bmim]Cl). The Cr(III)‐Al₂O₃ catalyst was characterized via XRD, DRS and Raman spectra and the results clarified the interaction between the Cr(III) and the alumina support. Meanwhile, the reaction solvents ([Bmim]Cl) collected after 1^st reaction run and 5^th reaction run were analyzed by ICP‐OES and LC‐ITMS and the results confirmed that no Cr(III) ion was dropped off from the alumina support during the fructose dehydration. Notably, Cr(III)‐Al₂O₃ catalyst had an excellent catalytic performance for glucose and sucrose and the HMF yields were reached to 73.7% and 84.1% at 120°C for 60 min, respectively. Furthermore, the system of Cr(III)‐Al₂O₃ and [Bmim]Cl exhibited a constant stability and activity at 100°C for 40 min and a favorable HMF yield was maintained after ten recycles.     

Conversion of d-glucose into 5-hydroxymethylfurfural (HMF) using zeolite in [Bmim]Cl or tetrabutylammonium chloride (TBAC)/CrCl2

The formation of hydroxymethylfurfural (HMF) from glucose was studied. It was found that the CrCl₂-catalyzed conversion in the ionic liquid, butylmethylimidazolium chloride ([Bmim]Cl) leads to negligible quantities of 3-deoxyglucosone confirming that fructose is the main intermediate. It was found that the environmentally unfriendly chromium salt could be replaced with zeolite (H-ZSM-5) leading to a 45% yield of HMF. It was also found that the solvent [Bmim]Cl could be replaced with non-toxic tetrabutylammonium chloride (TBAC) giving a 56% yield of HMF.