Tianjin Key Laboratory of Applied Catalysis Science and Technology and State Key Laboratory of Chemical Engineering, School of Chemical Engineering, Tianjin University, Tianjin, PR China.
ChemSusChem. 2010 Mar 22;3(3):350-5. doi: 10.1002/cssc.200900224.
The dehydration of D-fructose and glucose has been studied with acidic ionic liquids as catalysts. A series of Brønsted-acidic ionic liquids has been synthesized and tested in the dehydration of D-fructose. The results showed that N-methyl-2-pyrrolidonium methyl sulfonate NMPCH(3)SO(3) and N-methyl-2-pyrrolidonium hydrogen sulfate NMPHSO(4) have high catalytic activity. Highly efficient and selective dehydration of D-fructose to 5-hydroxymethylfurfural (HMF) was achieved in dimethyl sulfoxide (DMSO) under mild conditions. For example, a 72.3 % yield of HMF with 87.2 % selectivity were obtained for 2 h at 90 degrees C in the presence of 7.5 mol % NMPCH(3)SO(3). The effects of the reaction temperature, time, and solvent were investigated in detail. The catalyst and solvent can be recycled for the dehydration of D-fructose. The Hammett method was used to determine the acidities of these ionic liquids, which indicated that the acidity and molecular structure have strong effects on the catalytic activity of ionic liquids. Based on the experimental results, a possible reaction mechanism for the dehydration of D-fructose is proposed.
已研究了酸性离子液体作为催化剂对 D-果糖和葡萄糖的脱水作用。合成了一系列 Brønsted 酸性离子液体，并在 D-果糖的脱水反应中进行了测试。结果表明，N-甲基-2-吡咯烷酮甲基磺酸盐NMP CH(3)SO(3)和 N-甲基-2-吡咯烷酮硫酸氢盐NMP HSO(4)具有很高的催化活性。在温和条件下，在二甲亚砜(DMSO)中，D-果糖高效、选择性地脱水生成 5-羟甲基糠醛(HMF)。例如，在 7.5 mol%NMP CH(3)SO(3)存在下，在 90°C 下反应 2 小时，HMF 的收率为 72.3%，选择性为 87.2%。详细考察了反应温度、时间和溶剂的影响。催化剂和溶剂可用于 D-果糖的脱水循环。采用哈米特方法测定了这些离子液体的酸度，表明酸度和分子结构对离子液体的催化活性有很强的影响。根据实验结果，提出了 D-果糖脱水的可能反应机理。
Molecules. 2018-8-31
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