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研究生:吳欣怡
研究生(外文):Hsin-Yi Wu
論文名稱:室溫離子熔液的合成及其在Diels-Alder反應的應用
論文名稱(外文):Synthesis of room temperature ionic liquids and their applications for Diels-Alder reactions
指導教授:孫亦文
指導教授(外文):I-Wen Sun
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學系碩博士班
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2003
畢業學年度:91
語文別:中文
論文頁數:36
中文關鍵詞:室溫離子熔液
外文關鍵詞:room temperature ionic liquidsDiels-Alder reactions
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  隨著環保意識的高漲,以具有揮發性低、不易燃及回收容易等特性的”綠色溶劑”-離子熔液來取代傳統有毒、揮發性高的有機溶劑是必然的趨勢。近年來,室溫離子熔液已被廣泛應用於合成反應中,並且已經可以達到與在一般有機溶劑中進行反應的同等效果甚至更佳。
  本篇論文是將含有烷類取代的咪唑類化合物加入鹵化鋅配製成室溫離子熔液EMIC-ZnCl2、C8MIB-ZnBr2、C8C8IB-ZnBr2,其中包含手性結構的室溫離子熔液C5MIB-ZnBr2。利用這些熔液作為溶劑暨催化劑來進行Diels-Alder反應,並且探討鹵化鋅劑量、反應時間、產率、產物選擇性(endo/exo)的關係。其中EMIC-ZnCl2=1:2的離子熔液對於環戊二烯與CH2=CHC(O)R類型的親二烯基的反應,都有良好的產率和endo/exo比例大於10的產物選擇性。EMIC-ZnCl2=1:2在環戊二烯與丙烯酸乙酯的反應,可以重複使用至少3次,而產率並無明顯減少的現象;但是手性室溫離子熔液對於產物的鏡像選擇性(enantiomeric excess)的效果不佳。
  In the search for cleaner technologies for chemical synthesis finding alternatives to toxic volatile organic solvents is a particular important goal. Room temperature ionic liquids(RTIL)which are nonvolatile, inflammable, and good solvation power, have attracted a lot of recent attention as a “green solvent” alternative.

  The use of RTIL as solvents for Diels-Alder reactions has been reported. In this thesis, RTILs(EMIC-ZnCl2、C8MIB-ZnBr2、C8C8IB-ZnBr2、chiral C5MIB-ZnBr2)form from 1,3-dialkylimidazolium halides and ZnX2 in 1:2 ratio are studied. We found that EMIC-ZnCl2 is air and moisture stable as solvent and Lewis acid catalyst leads to dramatic enhancements of rate and stereoselectivity. For example, the reactions between cyclopentadiene and dienophiles(ethyl acrylate、MVK)to give a mixture of endo and exo products in a ratio selectivity up to 10:1. At the end of the reaction the product also forms a separate phase on top of the ionic liquid and is easily separated then washing with a small amount of ethyl ehthr and chloroform, which then allows reuse of the ionic liquid catalyst. For example, the reaction between cyclopentadiene and ethyl acrylate could be repeated at least three times with no noticeable drop in activity or yield.

  Further study to probe the effect of chiral functionalised ionic liquid C5MIB-ZnBr2 and such group with no significant entiomeric effect on the course of the Diels-Alder reactions.
中文摘要………………………………………………………………I
英文摘要………………………………………………………………II

第一章 緒論
  1-1 離子熔液的定義……………………………………………1
  1-2 離子熔液的簡介……………………………………………4
  1-3 室溫離子熔液的性質………………………………………5
  1-4 離子熔液在合成上的應用…………………………………8
  1-5 研究動機……………………………………………………13

第二章 結果與討論
  2-1 咪唑類化合物的合成………………………………………14
  2-2 鹵化鋅離子熔液的合成……………………………………16
  2-3 在離子熔液中的Diels-Alder反應 ………………………16
  2-4 再使用性的探討……………………………………………23

第三章 結論……………………………………………………………25

第四章 實驗……………………………………………………………26

第五章 參考資料………………………………………………………33
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