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研究生: 辜政脩
Ku, Cheng-hsiu
論文名稱: 壹:以雙乙醯丙酮基氧鈦錯合物催化酯基交換反應之研究, 貳:以N-亞柳胺基酸衍生之氧釩錯合物對稱催化二萘酚氧化偶合之研究
(I) A new transesterification protocol is developed by using TiO(acac)2 as the catalyst. (II) A series of chiral oxovanadium complexes serve
指導教授: 陳建添
Chen, Chien-Tien
學位類別: 博士
Doctor
系所名稱: 化學系
Department of Chemistry
論文出版年: 2003
畢業學年度: 91
語文別: 中文
論文頁數: 100
中文關鍵詞: 氧鈦雙乙醯丙酮基防曬油酯基交換催化親核性醯基取代防腐劑製程甲基酯與胺類和硫醇類反應性專一
英文關鍵詞: transesterification, TiO(acac)2, industrial applications, anti-oxidants, sun blocks, oxovanadium, BINOL, couplings of 2-naphthols
論文種類: 學術論文
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  • 中文摘要
    我們已開發出利用氧鈦雙乙醯丙酮基催化酯基交換。利用一莫耳百分率之催化量,以甲苯或二甲苯為溶劑,相同當量比之醇類與酯類反應下具有良好的反應性以及化學產率,不但可適用於醇類,更可應用於胺類,以及硫醇類等親核性試劑之交換反應,對於一級醇類不但反應快速,而且反應性專一產率高 ( 90-100 %),不會有其他副反應產生,在不同官能基取代之酯類或醇類均有良好之反應性與選擇性。至於二級醇類亦有相當高之應用價值產率 ( 85-90 %), 而對於甲基酯與胺類和硫醇類之親核性醯基取代反應,亦有合理的之產率,以及獨特性,若依照不同之酯類而作之酯基交換,更有不同之應用性,而其應用性包含工業界之高分子化合物製程,防腐劑製程,以及防曬油之製成,皆已達到相對可應用之產率。
    N-亞柳胺基酸三牙配子衍生之氧釩錯合物在不對稱催化2-萘酚氧化偶合,以2-羥基-1-苯并柳醛和2-胺基異戊酸(或苯丙胺酸)所衍生而成的氧釩(IV)錯合物以及以甲醇在結晶後氧釩(V)錯合物之為催化劑,可以得到1,1’-雙萘酚,產率可達70~100%,和達68%的鏡像選擇性,產物經在結晶後可應用於合成具高鏡像純度之手性1,1’-雙萘酚。

    Abstract
    We have developed a new transesterification protocol. by using TiO(acac)2 as the catalyst. Alcohols, amines, and thiols can be employed as protic nucleophiles to effect nucleophic acyl substitution of methyl esters. For primary and secondary alcohols the resultant transesterification products can be obtained with good to excellent chemical yields ( 85-100 %) without any side reactions. The new catalytic system may be potentially useful in industrial applications, including preparation of polyesters and polyamides, cosmetic and engineering anti-oxidants, and sun blocks.
    A series of chiral oxovanadium (IV) and oxovanadium (V) complexes obtained after recrystallization can be synthesizied from tridentate 3,5-substituted and 3,4-benzo- and 5,6-benzo- N-salicylidene -α-amino acids. They serve as efficient catalysts for the enantioselective oxidative couplings of 2-naphthols under O2 .The resultant BINOLs were obtained in good yields ( 70-100 % ) and with enantioselectivities of up to 68% In addition, they can be easily upgraded to optically pure BINOLs by recrystallization.

    目錄 中文摘要 英文摘要 第一章:以雙乙醯丙酮基氧鈦錯合物催化酯基交換反應之研究 第壹節 : 序論 第貳節 : 文獻回顧 第二章:以雙乙醯丙酮基氧鈦錯合物催化酯基交換反應之 研究結果與討論 第三章:以N -亞柳胺基酸衍生之氧釩錯合物對稱催化二萘酚 氧化偶合之研究 第壹節 : 序論 第貳節 : 文獻回顧 第四章:以N -亞柳胺基酸衍生之氧釩錯合物對稱催化二萘酚 氧化偶合之研究結果與討論 第五章:實驗步驟和光譜數據 第壹節:分析儀器 第貳節:實驗步驟及光譜數據 附錄: 參考文獻 1H NMR 光譜圖 13C NMR 光譜圖

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