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研究生: 陳盈成
Chen, Ying-Cheng
論文名稱: 氧-取代的醯胺肟環加成反應的研究
Investigation of Cycloaddition Reaction of O-Substituted Amide Oxime
指導教授: 簡敦誠
Chien, Tun-Cheng
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2017
畢業學年度: 105
語文別: 中文
論文頁數: 25
中文關鍵詞: 環化反應含氮雜環鐵試劑
英文關鍵詞: O-substituted amide oxime
DOI URL: https://doi.org/10.6345/NTNU202202360
論文種類: 學術論文
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  • 本研究希望以amide oxime作為起始物進行環化反應來得到含氮雜環分子,研究初期希望以amide oxime與ethyl propiolate進行[3+2]環化加成反應得到五元環含氮雜環,卻意外的發現得到[3+3]環化加成產物2-phenylpyrimidin-4-one,但同時也發現,副反應ethyl propiolate進行[2+2+2]環化加成的反應速率大於[3+3]環化反應的速率,導致研究無法繼續下去。在篩選各種dipolarophic等同物後,發現使用enaminones化合物代替ethyl propiolate得到[3 + 2]環化產物imidazoles衍生物。接著進行後續反應條件優化探討,發現以O-substituteds amide oxime作為起始物與enaminones化合物在催化當量的鐵試劑條件下,成功合成出各種不同取代的imidazoles衍生物。

    關鍵字:環化反應,含氮雜環,鐵試劑。

    In this study, we used amide oxime as a starting material for cyclization reaction to obtain nitrogen-containing heterocyclic molecules. In the beginning of the study, we anticipated that the amide oxime and ethyl propiolate could undergo [3+2] cycloaddition to afford the five-membered ring nitrogen-containing heterocycls. However, we found that the reaction rate of the side reaction, [2+2+2] cycloaddition of ethyl propiolate to triethyl 1,3,5-benzenetricarboxylate, is greater than the rate of heterocycle formation, which surprisingly formed the six-membered heterocycle, 2-phenylpyrimidin-4-one, instead. After screening of various dipolarophile equivalents, we found that the use of the enaminones compound instead of ethyl propiolate gave the [3+2] cyclized product, and the cyclization adduct was found to be imidazole derivatives After the successful cyclization reaction, the subsequent optimization conditions were discussed. Finally, we found that using O-substituted amide oxime as the starting material reacted with enaminones in the catalytic amount of iron reagent can undergo [3+2] cycloaddition which successfully formed a variety of different substituted imidazole derivatives.

    Keywords : O-substituted amide oxime, cycloaddition, enaminones, imidazole.

    目錄 Abstract i 摘要 ii 試劑縮寫對照表 iii 第一章 緒論 4 1.1 前言 4 1.2 具有imidazole (咪唑) 結構之天然物介紹 5 1.2.1 Imidazole衍生物 (胺基酸) 6 1.2.2 Imidazole衍生物 (海洋生物鹼) 7 1.3 具有imidazole (咪唑) 結構之臨床用藥介紹 7 1.4 具有生物活性之imidazole (咪唑) 衍生物之研究 8 第二章 文獻回顧 10 2.1 Imidazole化合物合成的研究 10 2.1.1 合成imidazole化合物的相關人名反應 10 2.1.2 合成imidazole化合物的反應 11 2.2 Amide oxime上的N-O鍵進行不對等性斷鍵的研究 18 2.2.1 利用aryl amide oxime上的N-O鍵斷鍵進行Tiemann重排的研究 18 2.2.2 利用N-aryl amide oxime上的N-O鍵斷鍵進行imidazole合成的研究 19 2.3 實驗動機與目的 21 參考文獻 24

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