Efficient Catalytic Conversion of Fructose into 5-Hydroxymethylfurfural in Ionic Liquids at Room Temperature
Efficient Catalytic Conversion of Fructose into 5-Hydroxymethylfurfural in Ionic Liquids at Room Temperature
复制标题
室温下离子液体中果糖高效催化转化为 5-羟甲基糠醛
DOI：
10.1002/cssc.200900199
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发表时间：
2009-01-01
期刊：
影响因子：
8.4
通讯作者：
Smith, Richard Lee, Jr.
中科院分区：
文献类型：
--
作者：
Qi, Xinhua;Watanabe, Masaru;Smith, Richard Lee, Jr.
建立一个使用生物质衍生碳水化合物化学的社会的主要挑战之一将是开发能够在室温下进行的快速有效的化学转化。在这里，我们报道了一种在室温下将果糖转化为5-羟甲基糠醛(5-HMF)的定量方法。从生物质来源的碳水化合物中制备5-HMF是一种多功能的、关键的可再生平台分子，被认为是碳水化合物化学中所需的必要转化。[1-3]已证明在水、[4]传统有机溶剂、[5，6]多相体系、[1-3]和离子液体(ILS)中通过酸催化果糖脱水生成5-HMF。[7-9]Dumesic和他的同事在1808℃的两相反应器系统中研究了酸催化的果糖脱水。[1]在果糖转化率为%的情况下，5-羟甲基呋喃的选择性最高可达85%。建立了在N，N-二甲基乙酰胺存在下，KI和H_2SO_4存在下，1008℃反应5 h，果糖转化为5-HMF的工艺，5-HMF的产率为92%。研究了离子液体转化果糖的反应，发现反应温度可降低到80~1408℃，反应时间可达数小时。赵埃塔尔。在离子液体溶剂(1-乙基-3-甲基咪唑氯，[EMIM][Cl])中，以CrCl2为催化剂，反应温度808℃，反应时间3h，5-HMF的收率达83%。研究了以1-丁基-3-甲基咪唑氯([BMIM][Cl])为催化剂，在1008℃下反应6h，果糖合成5-HMF的反应条件，反应温度高于808℃时，5-HMF的产率可达96%。
One of the main challenges for establishing a society that uses biomass-derived carbohydrate chemistry will be the development of effective chemical transformations that are rapid and that can be performed at room temperature. Herein, we report a method for transforming fructose into 5-hydroxymethylfurfural (5-HMF) that is quantitative and operates at room temperature. The preparation of 5-HMF, which is a versatile, key renewable platform molecule from biomass-derived carbohydrates, is regarded as an essential transformation needed in carbohydrate chemistry.[1–3] The formation of 5-HMF by the acid-catalyzed dehydration of fructose has been demonstrated in water,[4] traditional organic solvents,[5, 6] multiphase systems,[1–3] and ionic liquids (ILs).[7–9] Dumesic and co-workers studied acid-catalyzed fructose dehydration in a two-phase reactor system at 1808C,[1] and achieved a maximum 5-HMF selectivity of 85% with 89% fructose conversion.[3] Binder et al. developed a process that converted fructose to 5-HMF in N, N-dimethylacetamide in the presence of KI and H2SO4 at 1008C for 5 h reaction time, and achieved a 5-HMF yield of 92%.[6] These reports indicate that the effective conversion of fructose into 5-HMF in water, organic solvents, and multiphase systems requires high reaction temperatures of 100 to 3008C. Ionic liquids have been studied for the transformation of fructose and it has been found that the reaction temperature can be lowered to temperatures ranging from 80 to 1408C for reaction times on the order of hours. Zhao etal. achieved a 5-HMF yield of 83% in an ionic liquid solvent (1-ethyl-3-methylimidazolium chloride,[EMIM][Cl]) with CrCl2 as catalyst at a temperature of 808C for a reaction time of 3 h.[9] Yong et al. studied the production of 5-HMF from fructose in 1-butyl-3-methyl imidazolium chloride ([BMIM][Cl]) using CrCl2 as catalyst, and 5-HMF yields of 96% were achieved at 1008C in 6 h reaction time.[7] Up until now, all of these processes have reported that temperatures above 808C were necessary for the transformation reactions, with some of the chief reasons being those related to the melting point of the ionic liquid or to the high viscosity of the reaction mixture.