单糖在咪唑基离子液体/DMSO-d6中构型分布的NMR研究
收稿日期: 2025-09-23
网络出版日期: 2025-12-10
基金资助
国家自然科学基金项目(22075308)
NMR Study of Tautomeric Distribution of Monosaccharides in Imidazolyl Ionic Liquids/DMSO-d6
Received date: 2025-09-23
Online published: 2025-12-10
单糖的构型分布可影响其转化和利用中的反应路径和产物选择性．以DMSO-d6为共溶剂，在25 ℃条件下通过定量1H NMR研究了单糖在咪唑基离子液体中的构型分布规律．结果表明，在酸性离子液体中，β-吡喃糖的平衡比例由大到小为：D-葡萄糖>D-氨基葡萄糖盐酸盐>N-乙酰-D-氨基葡萄糖>D-甘露糖．D-果糖在[HSO3-BMIM]HSO4中几乎完全转化为5-羟甲基糠醛（由呋喃糖反应生成），在其他离子液体中平衡后呋喃糖的比例甚至高于吡喃糖的比例．两性金属氯化物与氟原子的引入可能会导致更高比例的呋喃糖的产生．[BMIM]BF4等的添加则可能会抑制单糖的构型转化．单糖构型分布的基础数据为生物质转化的离子液体的选择与设计提供了指导．
刘佳 , 王英雄 , 赵建成 . 单糖在咪唑基离子液体/DMSO-d6中构型分布的NMR研究[J]. 波谱学杂志, 2026 , 43(2) : 146 -163 . DOI: 10.11938/cjmr20253182
The tautomeric distribution of monosaccharides could influence reaction pathways and product selectivity during their conversion and utilization. Using DMSO-d6 as cosolvent, we investigated the tautomeric distribution of monosaccharides in imidazolyl ionic liquids at 25 ℃ by quantitative 1H NMR. In acidic ionic liquids, the results indicate that the proportion of β-pyranose after equilibrium decreases in the following order: D-glucose > D-glucosamine hydrochloride > N-acetyl-D-glucosamine > D-mannose. D-fructose is almost completely converted to 5-hydroxymethylfurfural (formed from the furanose) in [HSO3-BMIM]HSO4. In other ionic liquids, the proportion of furanose even exceeds that of pyranose after equilibrium. The introduction of amphoteric metal chloride and fluorine may lead to a higher proportion of furanose. The addition of [BMIM]BF4 and other reagents may inhibit the tautomeric conversion of monosaccharides. The fundamental data on monosaccharide tautomer distribution can guide the selection and design of ionic liquids for biomass conversion.
Key words： monosaccharides; imidazolyl ionic liquids; NMR; tautomeric distribution
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