标题：Theoretical study on the mechanism of the side reaction of 1-butyl-3-methylimidazolium cation with D-glucose
作者：Wei, Xiaofeng; Han, Zhe; Zhang, Dongju
作者机构：[Wei, Xiaofeng; Zhang, Dongju] Shandong Univ, Dept Chem & Chem Engn, Jinan 250100, Peoples R China.; [Wei, Xiaofeng] Shandong Univ, Environm Res Ins 更多
通讯作者地址：[Zhang, DJ]Shandong Univ, Dept Chem & Chem Engn, Jinan 250100, Peoples R China.
关键词：Imidazolium-based ionic liquids; Cellulose chemistry; Reaction; mechanism; DFT
摘要：To understand the non-inert nature of ionic liquids in cellulose chemistry, density functional theory calculations were carried out to investigate the reaction of 1-butyl-3-methylimidazolium cation ([bmim](+)) with model compounds alpha- and beta-glucoses (the basic units of cellulose and its degradation products) in the absence and presence of base, triethylamine (TEA). The calculated energy barriers for the reactions of [bmim](+) with alpha- and beta-glucoses without TEA were 67.97 and 66.19 kcal mol (1), respectively. With the assistance of TEA, the barriers were reduced to 48.17 and 46.96 kcal mol (1), due to the enhanced electrophilic abilities of H-6 and nucleophilic abilities of C-2 induced through deprotonation of the C-2 atom, respectively. The present results rationalize the experimental finding well and provide a clear explanation on why imidazolium-based ionic liquids are considered as non-inert solvents in cellulose chemistry. (C) 2013 Elsevier Ltd. All rights reserved.