【作者】 卓耀文；

【导师】 张正波；

【作者基本信息】 华中科技大学 ， 有机化学， 2007， 硕士

【摘要】 室温离子液体因其独特的物理化学性质,被认为是替代常用挥发性有机溶剂的绿色溶剂。近年来,离子液体的研究开始向功能化的方向发展,即对离子液体进行性能改进以达到特定的需求。将手性引入至离子液体中是离子液体功能化的一个重要方法,手性离子液体因其在手性识别、不对称合成和手性催化方面的应用而受到广泛关注。但是到目前为止,手性离子液体的合成大多数都是在阳离子上引入手性基团,在阴离子上引入手性基团的并不多见。本文从天然氨基酸出发,通过酯化、磺酰化反应合成出三种全氟丁基磺酰氟修饰的手性阴离子:N-全氟丁基磺酰化丙基酸甲酯[I-Ala]、N-全氟丁基磺酰化亮基酸甲酯[I-Leu]和N-全氟丁基磺酰化缬基酸甲酯[I-Val],同时以N-甲基咪唑为原料合成出1-甲基-3-乙基咪唑盐[emim]OH,将手性阴离子与[emim]OH进行酸碱中和反应,合成出一系列以N-全氟丁基磺酰化氨基酸甲酯为阴离子,[emim]+为阳离子的新型手性离子液体[emim][I-Ala]和[emim][I-Val]。本文还对反应条件进行了研究,建立了一条合成此类新型手性离子液体的新方法。同时也对该手性离子液体的光学纯度测定进行了一些探索。实验结果表明,在低温,不加任何缚酸剂和溶剂的情况下,氨基酸甲酯与全氟丁基磺酰氟的磺酰化反应能顺利进行,且因为反应体系只有两种化合物,在此条件下的后处理方法简单,使得产物的分离更加便利。由此合成得到的手性离子液体在室温下均为液体,为以后用于手性合成打下了基础。更多还原

【Abstract】 Because of their unique physical and chemical properties, room temperature ionic liquids(RTILs) are now expected to be an alternative to conventional volatility solvents for organic reactions.Recently, design and synthesis of RTILs with controllable physical and chemical properties or even specific functions has been developed for specifically requirements. Combine chiral with ionic liquids is an important way of the function of ionic liquids. People focused on the synthesis of chiral ionic liquids(CILs) for their particularly potential applications to chiral discrimination, including asymmetric synthesis and chiral catalysis. But up to now,most of CILs are derived from chiral cations, only part of them derived from chiral anions.In this paper, a series of chiral ionic liquids([emim][I-Ala],[emim][I-Val]) composed of 1-ethyl-3-methylimidazolium cation([emim]) and chiral anions derived from natural amino acids modified with perfluorobutylsulfonyl groups were synthesized through the acid-base reaction.Three chiral anions: N-perfluoroethyl- sufonyl alanine ethyl ester([I-Ala]) and N-perfluoroethylsufonyl valine ethyl ester([I-Val]) and N-perfluoroethylsufonyl leucine ethyl ester([I-Leu]) were synthesized from amino acids through esterification and sulfonylation. A new method was builded to synthesize these CILs through improving the condition of reactions. The optical activity of CILs were also detected.The results of experiment showed amino acid methyl esters could react easily with perfluorobutylsulfonyl fluoride without any solvents and catalyzer in low temperature. Product could be separated easily from reaction system using a simple method as there were only two reagent in the reaction system. All of the CILs synthesized in this paper could be used in chiral synthesis as they had low melting point and optical activity.更多还原