臺灣博碩士論文加值系統

摘要
有機金屬在近幾十年來已被廣泛地應用於有機合成反應上，不論是用於分子間的偶合反應、分子的環化或是開環反應，有機金屬在有機合成的應用上已不可或缺了。在有機金屬催化反應領域裡，不但能具有好的化學位向選擇性，也能有好的立體位向選擇性。在天然物這種需要精準控制位向的合成中，有機金屬扮演著重要的角色。
本論文著重於釕金屬以及鋅金屬應用於丙炔醇官能基的轉化反應。包含第一部分：釕金屬應用於氫原子的轉移反應(Ruthenium-Catalyzed Transformation of Propargyl Ether into 1,3-Dienes and Benzaldehyde via Transfer Hydrogen) , ，第二部分：釕金屬應用於碳碳三鍵的裂解反應(Ruthenium-Catalyzed Cleavage of a Carbon-Carbon Triple Bond: Efficient Transformation of Propargyl Alcohols into Alkenes and Carbon Monoxide) ，以及第三部份：鋅錯合物應用於環化反應(Zinc-Catalyzed Cyclization from Propargyl Alcohols) 。這些反應，不但在溫和條件下即可進行反應，而且只需5 %的催化劑量就可以完成反應。因此，應用於有機合成時，對環境造成的污染很低，可以說是符合綠色化學的精神。
在材料應用方面，液晶顯示器在近幾年來蓬勃地發展，但是因為其偏光膜是屬於O-型偏光膜，最大的缺點即是其視角很小。而改善視角有許多方法，例如：增加廣視角膜或是補償膜。但是，多一層膜的製備不但成本增加，其亮度也會下降。因此，本論文在材料部份，將著重於研發圓盤型分子，將圓盤型分子應用於E-型偏光膜上。除了在製程上可以節省成本，也可以大大改善視角。在未來的發展是很有潛力的。

Abstract

Organometallics plays an essential role on organic synthesis in these decades. It was applied in coupling reactions, cyclization reactions or ring opening reactions. Organometallics catalyzed reactions not only have good regioselectivities but have good stereoselectivities. In natural products synthesis, it is very important to control stereo or regio direction in specific positions.
We emphasize on ruthenium and zinc metal complex which apply in ethynyl alcohol catalyzed transfer reactions. First, ruthenium complex was applied on transformation of propargyl ether into 1,3-dienes and benzaldehyde via transfer hydrogen. Second, ruthenium complex was apply on cleavage of a carbon-carbon triple bond: efficient transformation of propargyl alcohols into alkenes and carbon monoxide. Last, we used zinc complex on cyclization from propargyl alcohols. These reactions worked on mild conditions and used less catalyst (5 %) without any other chemical reagents to complete the reactions. These new reactions chemistry is Green Chemistry.
Liquid crystal display (LCD) was developed full of vitality during decades. Because of the O-type polarizer, one drawback of the LCD is the narrow of the view angel. Although compensation film can improve the view angle, it critically reduces the backlight and increases the cost. We synthesis disk molecules to apply in E-type polarizer. E-type polarizer not only can increase the view angel, but also reduce the cost.

第一章 有機金屬催化反應……………………………………………1
1-1 序論………………………………………………………………1
1-2 釕金屬催化氫原子轉移反應……………………………………2
1-2-1 氫原子轉移反應應用於非環狀醚類分子…………………4
1-2-2 氫原子轉移反應應用於環狀醚類分子…………………11
1-2-3 釕金屬催化氫原子轉移之反應機構……………………13
1-2-4 結論………………………………………………………16
1-2-5 實驗及光譜數據部份……………………………………17
1-2-5-1 本論文實驗中藥品之中英文對照…………………17
1-2-5-2 實驗的一般操作……………………………………20
1-2-5-3 實驗步驟及光譜數據………………………………22
1-3 釕金屬催化碳碳三鍵裂解反應………………………………47
1-3-1 釕金屬催化丙炔醇裂解成烯類及一氧化碳最佳化條件48
1-3-2 釕金屬催化丙炔醇裂解成烯類及一氧化碳……………50
1-3-3 釕金屬催化丙炔醇裂解成烯類及一氧化碳之反應機構53
1-3-4 結論………………………………………………………55
1-3-5 實驗及光譜數據部分……………………………………56
1-4 鋅金屬催化環化反應…………………………………………60
1-4-1鋅金屬催化丙炔醇環化生成酮類衍生物………………63
1-4-2鋅金屬催化丙炔醇環化生成酮類衍生物反應機構………66
1-4-3 鋅金屬催化丙炔醇環化生成芳香環反應………………68
1-4-4鋅金屬催化丙炔醇環化生成芳香環反應機構……………73
1-4-5 結論………………………………………………………74
1-4-6 實驗及光譜數據部分……………………………………75
1-5 參考文獻………………………………………………………91
第二章 有機碟狀聯苯分子應用於E-型偏光片研發…………………1
2-1 序論………………………………………………………………1
2-2 分子設計…………………………………………………………5
2-2-1 對稱型HBC(D6h)之合成方法………………………………8
2-2-2 不對稱HBC(D2h)之合成方法……………………………11
2-3 光譜分析及性質探討……………………………………………15
2-3-1 紫外光光譜………………………………………………15
2-3-2 液晶特性及物理性質的探討……………………………19
2-3-3薄膜的製備………………………………………………21
2-4 結論………………………………………………………………25
2-5 合成步驟及光譜資料……………………………………………26
2-6 參考文獻…………………………………………………………42

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