臺灣博碩士論文加值系統

由陰陽離子所組合而成的離子液體，具有耐強酸、耐高溫、穩定性佳、可再回收使用等優點；以及高極性、極低蒸氣壓的特性。近年來廣泛應用於有機反應。我們設計了具有雙環結構的離子液體[b-3C-im][NTf2]，其具有[3,3,0]雙環之剛性結構，與文獻上最常使用的離子液體[bmim][PF6]相比較穩定性有大幅的改良，這個新的化學穩定之疏水性室溫離子液體，隨後將應用於有機合成中。
我們藉由離子液體[b-3C-im][NTf2]搭配微波，加速Pictet-Spengler反應，縮短四氫-β-乙內醯衍生物的合成時間。接著我們也將[b-3C-im][NTf2]離子液體應用於Claisen 重排反應，發現應用於合成酪氨酸衍生物只需要兩分鐘左右即可完成，且產率也不錯。

Ionic liquids are solvent systems that consist of cations and anions at ambient temperature. Its high polarity, low melting point, both thermal and chemical stability, and negligible vapor pressure properties have emerged as attractive alternatives to conventional organic solvents. We designed ionic liquid, [b-3C-im][NTf2], which has a novel and rigid structure. The ionic liquid is not only chemically stable, but also has a low melting point, low water content, and dynamic viscosity. Additionally, this new ionic liquid was applied, in conjunction with focused microwaves, to the two-step synthesis of tetrahydro- β-carbolinehydantions. We have also used [b-3C-im][NTf2] and microwaves to suceed in the rapid synthesis of tyrosine derivatives with good overall isolated yields.

第一章 離子液體....................................................................................1
1. 離子液體背景介紹.......................................................................1
2. 離子液體在有機反應中的應用...................................................3
2.1 在離子液體中進行Heck 反應8 .......................................4
2.2 以含釕金屬之離子液體進行RCM 反應9 .......................5
2.3 在離子液體中進行一鍋式反應合成?hydroxylamino
phosphonate 衍生物10 ..................................................................5
3. 離子液體真的很穩定?.................................................................6
4. 文獻中對離子液體之穩定性改良...............................................7
5. 本實驗室對離子液體之化學穩定性改良..................................8
6. 總論.............................................................................................13
7. 參考文獻.....................................................................................14
第二章 新一代離子液體的設計與製備................................................15
1. 研究動機.....................................................................................15
2. 結果與討論.................................................................................17
3. 結論.............................................................................................21
4. 實驗部份.....................................................................................22
4.1 實驗一般描述..................................................................22
II
4.2 實驗藥品..........................................................................23
4.3 實驗步驟..........................................................................24
4.4 實驗圖譜..........................................................................33
5. 參考文獻.....................................................................................51
第三章 四氫-β-乙內醯衍生物................................................52
1. 四氫-β-乙內醯衍生物生物活性簡介........................52
2. 四氫-β-乙內醯衍生物合成簡介................................54
3. 結果與討論.................................................................................57
4. 結論.............................................................................................60
5. 實驗部分.....................................................................................60
5.1 實驗一般敘述..................................................................60
5.2 實驗藥品..........................................................................62
5.3 實驗步驟..........................................................................63
5.4 光譜數據與圖譜..............................................................65
6. 參考文獻...................................................................................122
第四章 Claisen 重排反應.....................................................................123
1. Claisen 重排反應之簡介..........................................................123
2. 結果與討論...............................................................................126
3. 結論...........................................................................................129
III
4. 實驗部份...................................................................................130
4.1 實驗一般描述................................................................130
4.2 實驗藥品........................................................................132
4.3 實驗步驟........................................................................133
4.4 光譜數據與圖譜............................................................136
5. 參考文獻...................................................................................213
附件一.....................................................................................................214
離子液體於有機合成文獻整理.....................................................214
附件二.....................................................................................................226
新一代離子液體開發與應用.........................................................226
附件三.....................................................................................................228
1-Butyl-2,3-trimethyleneimidazolium bis(trifluoromethylsulfonyl)
imide ([b-3C-im][NTf2]): a new, stable ionic liquid .......................228

第一章 離子液體
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第二章 新一代離子液體的設計與製備
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第四章 Claisen 重排反應
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