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研究生: 蔡昊諭
Tsai, Hao-Yu
論文名稱: 碘催化2-苯乙烯醛與吲哚反應通過親核加成/4π-電環化/異構化序列合成 1H-茚 化合物類衍生物
Iodine-Catalyzed Reactions of 2-Styrylaldehydes With Indoles for the Synthesis of 1H-Indene Derivatives via a Nucleophilic Addition/4π-Electrocyclization/Isomerization Sequence
指導教授: 姚清發
Yao, Ching-Fa
口試委員: 柳如宗
Liu, Ju-Tsung
林文偉
Lin, Wen-Wei
姚清發
Yao, Ching-Fa
口試日期: 2023/07/21
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2023
畢業學年度: 111
語文別: 中文
論文頁數: 219
中文關鍵詞: 吲哚電環化親核加成異構化序列
英文關鍵詞: indole, indene, electrocyclization, nucleophilic addition, isomerization sequence
研究方法: 實驗設計法
DOI URL: http://doi.org/10.6345/NTNU202301302
論文種類: 學術論文
相關次數: 點閱:41下載:2
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  • 茚是一類重要的分子,它不僅引起有機化學家的興趣,因為大量天然和合成化合物含有其特殊骨架而且皆能表現出生物活性或藥物活性,除此之外茚在材料科學也有了相當大的應用與發展,例如在光伏太陽能電池和新型螢光材料的製備。在過去的幾年裡,化學家已經開發了許多方法來構建這種雙環系統,其中探索最多的兩種是涉及分子內弗里德爾-克來福特反應的陽離子過程,以及過渡金屬在組裝茚框架中起關鍵作用的過程。
    而本篇論文研究的方向則是利用路易士酸的催化以及電環化過程,來構築中心骨架的茚結構,並藉由接上保護基來產生單一反式結構的起始物,其中可透過探討不同取代基作為親電子基在合環時對於4π電子對的影響,進而發現可利用熱力學的趨勢,得到較穩定的主產物,甚至衍生出對於不同的吲哚作為親核基的探討, 並利用聚焦式微波合成儀將反應時間控制,因為其穩定的加熱模式,進一步從結果探討對於1-甲基-3-(2-苯基-1H-茚-3-基)-1H-吲哚的高度單一反應性。

    Indene is an important type of molecule that not only attracts the interest of organic chemists, as a large number of natural and synthetic compounds contain their unique skeletons and can exhibit biological or pharmaceutical activity. In addition, indene has also made significant applications and developments in materials science, such as in the preparation of photovoltaic solar cells and new fluorescent materials. In the past few years, chemists have already developed many methods to construct such a bicyclic system, of which the two most explored are the cationic processes involving intramolecular Friedel-Crafts reaction, and the process in which transition metals play a key role in assembling the indene framework.
    The research direction of this paper is to use the catalysis and electrocyclization process of Lewis acid to construct the indene structure of the central skeleton, and to generate a single trans structure starting material by connecting protective groups. By exploring the influence of different substituents as electrophilic groups on 4 π electron pairs during ring formation, it is found that thermodynamic trends can be utilized to obtain more stable main products, Even exploring different indoles as nucleophilic groups has been derived, and the reaction time has been controlled using a focused microwave synthesizer due to its stable heating mode, further exploring the highly single reactivity of 1-methyl-3- (2-phenyl-1H-inde-3-yl) -1H indole from the results.

    謝誌i 中文摘要 iii Abstract iv 1.前言1 1-1. 製備茚(1H-indene)衍生物文獻回顧3 1-1-1.陽離子過程-基於分子內 Friedel-Crafts 反應的方法3 1-1-2.過渡金屬 (TM) 催化過程6 1-1-3.鄰位取代苯基乙炔的環化反應 10 1-1-4.有機催化方法11 1-2. 微波簡介13 2.研究策略及構想 14 3.實驗結果與討論 16 3-1. 有關化合物3-(2-苯基-1H-茚-1-基)-1H-吲哚的探討16 3-2. 起始物(E)-2-苯乙烯基苯甲醛的製備18 3-3. 關於化合物1-甲基-3-(2-苯基-1H-茚-3-基)-1H-吲哚 3aa的最佳化條件探討22 3-4. 反應機構的探討25 3-5. 不同(E)-2-苯乙烯基苯甲醛取代基受質測試30 4.結論37 5.實驗方法38 5-1.分析儀器及基本實驗操作38 5-2.實驗步驟 40 6.參考資料45 7.光譜資料48

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