壹、利用氧鉬錯合物催化1,3-雙硫縮醛衍生物及醯化醣類選擇性去保護之研究. 貳、以螺旋喹喔啉發光單元與醣類混成系統作為發光型光學膜材料之研究

陳慧玲(Hui Ling, Chen)

指導教授 ： 陳建添

國立臺灣師範大學/理學院/化學系/碩士(2009年)

摘要

本論文第一部分利用二氯二氧鉬金屬錯合物 (MoO2Cl2) 催化1,3-雙硫縮醛衍生物去保護反應。基於實驗室先前的研究成果，我們利用三氟甲基磺酸氧釩錯合物 (VO(OTf)2) 當作催化劑，製備雙硫縮醛或酮類衍生物，在二氯二氧鉬金屬錯合物催化1,3-雙硫縮醛去保護反應中作為受質，之後我們也將先前以 VO(OTf)2 催化去雙硫縮醛保護結果與本次利用 MoO2Cl2 催化做比較。
由於二氯二氧鉬金屬錯合物 (MoO2Cl2) 具有不錯的催化效果，於是我們也應用在醯化醣類衍生物選擇性去保護方面。我們將醣類引入不同的醯基保護，之後利用 MoO2Cl2 當作催化劑 ，在甲醇當中進行選擇性去乙醯，並保留部分位置的其他醯基保護，並且可將選擇性去保護之產物，利用於光學膜單元分子之合成。
本論文第二部分是將本實驗室已發展出來的喹喔啉發光單元衍生，與醣類混成系統作為發光型光學膜材料的研究。在喹喔啉的 C5 和 C8 位置引入疊氮，然後以速配組合化學 (Click chemistry) 的方式，與醣類衍生物結合形成光學膜發光單元。之後藉由二氯二氧鉬金屬錯合物催化水解三醋酸纖維素 (cellulose triacetate)，引入末端炔結構後期望作為發光膜載體，之後嘗試發展光學膜材料的研究。

關鍵字

氧鉬金屬 ； 雙硫基保護 ； 醯化醣類 ； 光學膜 ； 選擇性去保護

並列摘要

In the first part of our project, molybdenum dichloride dioxide was used to catalyze the deprotection of the 1,3-dithiane compounds. Our previous studies have shown that vanadyl triflate can act as a catalyst to convert aldehydes or ketones into 1,3-dithianes, Which were use for subsequent deprotection studies. Here, we compare the ability of vanadyl triflate with molybdenum dichloride dioxide as catalysts for the deprotection of the 1,3-dithiane compounds.

In addition, molybdenum dichloride dioxide was examined as the catalyst to selectively deprotect peracetylated carbohydrates bearing other acyl groups. The carbohydrates were first acylated by different acyl groups, and then selectively deacetylated in MeOH by MoO2Cl2. The deprotection process proceeded smoothly leaving other acyl groups (like benzonyl, pivaloyl, or t-Boc) intact. Subsequently, a couple of the products could be applied to synthesize the basic unit of optical film materials.

In the second part of our project, integration of quinoxaline-based fluorophore and carbohydrate into hybrid fluorescent optical film systems was explored template. We introduced terminal azides to both the C5 and C8 positions of a quinoxaline which was developed as a OLED units in our lab. Through Click chemistry, carbohydrates bearing terminal propargyl units were integrated with the quinoxaline by cycloaddition. Suitable diaceylated cellulose (DAC) as prepared by selective a deacetylation of TAC as cat. By MoO2Cl2. The unmasked 1o hydroxyl group was transformed into a carbamate bearing a terminal alkyne. The product was used further as a critical material for fabricating fluorescent optical films, with the Q-LED by click chemistry.

參考文獻

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