研究生: |
吳貞宜 Jhenyi Wu |
---|---|
論文名稱: |
酯類上烷氧殘基之自由基反應性研究 Radical Reactions in Esters with Alkoxy Functionality Chemistry. An Unusual Alcohol Moiety Hydrogen-Abstraction. |
指導教授: |
姚清發
Yao, Ching-Fa |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2004 |
畢業學年度: | 92 |
語文別: | 中文 |
論文頁數: | 120 |
中文關鍵詞: | 酯類 、硝基苯乙烯 、自由基 、烷氧殘基 、加成-脫去 |
英文關鍵詞: | esters, nitro styrenes, radical, alkoxy moiety, addition-elimination |
論文種類: | 學術論文 |
相關次數: | 點閱:173 下載:0 |
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本研究為利用常見的自由基誘發劑-過氧化苯甲醯基 (Benzoyl peroxide),將酯類之烷氧殘基以具立體選擇性的方式引入,合成3-芳香基丙烯酯類衍生物。其反應機構首先係利用過氧化苯甲醯基於高溫下裂解形成自由基,再利用它拔取酯類烷氧殘基上的氫原子,所形成之自由基進一步加成至(E)--硝基苯乙烯((E)--Nitrostyrene)系列物,最後脫去二氧化氮自由基(NO2‧)可得一系列3-芳香基丙烯酯類化合物。
反應過程中,除了高立體選擇性外,也具有中至高產率的結果。同時可使用具有不同取代基之(E)--硝基苯乙烯系列物,與含不同立障的烷氧殘基之酯類,來置備各式各樣的(E)-苯乙烯酯類,此策略及結果可充分驗證本反應的應用價值。
最後,本研究利用乙酸丙酯(Propyl acetate),在相似反應條件下,與受質(E)-2,6-雙甲氧基--硝基苯乙烯反應,將分離得到之’位向取代的產物,進一步利用氫氧化鋰水解後,形成之(E)-苯丁烯醇為天然物中具活性之特徵結構。因此,此步驟簡單,產率亦較文獻報導高出許多之自由基加成-脫去反應,應用在合成具有生物活性之相關衍生物,為本研究最終目標與極富價值性之發展;另外,本論文部分結果也已發表於Tetrahedron Letters 2004, 45, 3685. 顯示其價值性已受肯定。
Various geometrically pure (E)-alkenes have been synthesized by radical substitution of alcohol moieties generated via hydrogen abstraction within ethyl esters. These reactions occurred with high regio-selectivity and gave a new access to 1-methyl-3-aryl-allyl esters.
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