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研究生: 陳慧玲
Hui Ling, Chen
論文名稱: 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
指導教授: 陳建添
Chen, Chien-Tien
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2009
畢業學年度: 97
語文別: 中文
論文頁數: 132
中文關鍵詞: 氧鉬金屬雙硫基保護醯化醣類光學膜選擇性去保護
論文種類: 學術論文
相關次數: 點閱:128下載:0
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  • 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。

    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.

    中文摘要 英文摘要 第一章、 緒論 第一節、氧鉬金屬錯合物在有機合成及催化反應之應用……………..1 壹、 背景…………………………………………………………………1 貳、 烯烴複分解反應 (olefin metathesis)………………………………1 參、 環氧化反應 (epoxidation)…………………………………………3 肆、 硫基轉移反應 (sulfur transfer reaction)…………………………...4 伍、 二氯二氧鉬金屬錯合物之應用……………………………………5 第二章、鉬氧金屬錯合物催化1,3-雙硫縮醛衍生物去保護反應 第一節、前言……………………………………………………………10 壹、 背景………………………………………………………………10 貳、 1,3-環雙硫縮醛衍生物之應用…………………………………..11 参、去除雙硫基醚類保護基之方法……………………………………16 ㄧ、酸和金屬催化水解 (acid and metal ion-mediated hydrolsis)..17 二、氧化或烷化方式水解 (oxidation or alkylation hydrolysis)….21 三、還原去雙硫醚基保護 (reductive deprotection)………………25 四、異相催化方式水解 (heterogeneous catalysis hydrolsis)...…...27 第二節、結果與討論……………………………………………………29 壹、1,3-雙硫縮醛類或酮類衍生物之製備方式………………………..29 貳、利用氧鉬錯合物催化1,3-雙硫縮醛類或酮類去保護過程……….30 参、氧釩及氧鉬錯合物催化1,3-雙硫縮醛類或酮類之比較………….35 肆、結論與展望…………………………………………………………37 第三章、鉬氧金屬錯合物催化醣類去乙醯基反應 第一節、前言……………………………………………………………39 壹、背景…………………………………………………………………39 貳、醯化衍生物之應用…………………………………………………39 参、脫除醯基保護的方法………………………………………………44 第二節、結果與討論……………………………………………………51 壹、醣類醯化之衍生物製備方式………………………………………51 貳、利用氧鉬錯合物催化醯化醣類選擇性去保護過程………………53 参、結論與展望…………………………………………………………60 第四章、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 第一節、前言……………………………………………………………61 壹、背景…………………………………………………………………61 貳、醣類1,3-二極環化衍生物之應用………………………………….64 第二節、結果與討論……………………………………………………69 壹、分子設計及合成……………………………………………………69 貳、發光膜單元分子之性質探討………………………………………74 参、結論與展望…………………………………………………………81 第五章、實驗步驟及光譜數據 第一節、分析儀器………………………………………………………83 第二節、催化1,3-雙硫縮醛衍生物去保護反應實驗步驟…………….86 2-1合成雙硫縮醛衍生物之ㄧ般步驟………………………86 2-2以氧鉬錯合物催化雙硫縮醛去保護之反應步驟………86 第三節、催化醣類去乙醯基反應實驗步驟……………………………96 3-1合成醣類醯化衍生物之ㄧ般步驟………………………96 3-2以氧鉬錯合物催化醯化醣類去保護之反應步驟……..103 第四節、化合物 37-58 合成方法及步驟……………………………104 第五節、參考文獻……………………………………………………..125 附錄 1H、13C光譜數據

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