Synthesis of the perdeuterated cellulose solvents 1-ethyl-3-methylimidazolium acetate (EMIM-OAc-d14) and 1-butyl-3-methylimidazolium acetate (BMIM-OAc-d18) and of 2-13C-butyl-3-methylimidazolium acetate
Synthesis of the perdeuterated cellulose solvents 1-ethyl-3-methylimidazolium acetate (EMIM-OAc-d14) and 1-butyl-3-methylimidazolium acetate (BMIM-OAc-d18) and of 2-13C-butyl-3-methylimidazolium acetate
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DOI：
10.1002/jlcr.1591
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发表时间：
2009-05
影响因子：
1.8
通讯作者：
Y. Yoneda;Gerald Ebner;T. Takano;F. Nakatsubo;A. Potthast;T. Rosenau
中科院分区：
文献类型：
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作者：
Y. Yoneda;Gerald Ebner;T. Takano;F. Nakatsubo;A. Potthast;T. Rosenau
描述了两种全氘化离子液体 (IL) 的合成，它们可用作纤维素衍生化和加工的溶剂：乙酸 1-乙基-3-甲基咪唑鎓 (EMIM-OAc-d14) 和乙酸 1-丁基-3-甲基咪唑鎓 (BMIM-OAc-d18)。靶标是通过三步序列从咪唑获得的，分别从丁基化和乙基化开始。纯化所得 1-烷基咪唑，随后根据新方案使用碳酸二甲酯-d6 进行甲基化。为了获得1-烷基-3-甲基咪唑鎓部分，1-烷基咪唑的甲基化被证明优于传统的1-甲基咪唑烷基化方法。添加乙酸-d4 导致碳酸甲酯抗衡阴离子无痕降解，并巧妙地交换为乙酸盐。 IL 2-13C-丁基-3-甲基咪唑乙酸盐，其中同位素富集的 C-2 是副反应和溶剂-溶质相互作用的良好 NMR 指示剂，根据相同的反应顺序合成，从 2-13C-1-烷基咪唑开始，而 2-13C-1-烷基咪唑又通过乙二醛、烷基胺、氨和多聚甲醛-13C 反应获得。版权所有 © 2009 约翰·威利父子有限公司
The syntheses of two perdeuterated ionic liquids (ILs), which have found use as solvents for cellulose derivatization and processing in addition, are described: 1-ethyl-3-methylimidazolium acetate (EMIM-OAc-d14) and 1-butyl–3-methylimidazolium acetate (BMIM-OAc-d18). The targets were obtained from imidazole in three-step sequences starting with butylation and ethylation, respectively. The resulting 1-alkyl imidazoles were purified, and subsequently methylated according to a novel protocol using dimethylcarbonate-d6. To obtain the 1-alkyl-3-methylimidazolium moiety, methylation of 1-alkylimidazoles proved to be superior to the conventional approach of alkylating 1-methylimidazole. Addition of acetic acid-d4 caused traceless degradation of the methylcarbonate counter anions, which were neatly exchanged for acetate. The IL 2-13C-butyl-3-methylimidazolium acetate, in which the isotopically enriched C-2 is a good NMR-indicator of side reactions and solvent–solute interactions, was synthesized according to the same reaction sequence, starting from 2-13C-1-alkylimidazole which, in turn, was obtained by reaction of glyoxale, alkylamine, ammonia and paraformaldehyde-13C. Copyright © 2009 John Wiley & Sons, Ltd.