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研究生：	黃琬澐 Huang, Wan-Yun
論文名稱：	應用丙烯基醋酸酯合成四取代之呋喃與萘併呋喃 Efficient Synthesis of Tetrasubstituted Furans and Naphthofurans by Using Nitroallylic Acetates
指導教授：	陳焜銘 Chen, Kwun-Min
學位類別：	碩士 Master
系所名稱：	化學系 Department of Chemistry
論文出版年：	2012
畢業學年度：	100
語文別：	中文
論文頁數：	49
中文關鍵詞：	丙烯基醋酸酯、四取代呋喃、萘併呋喃、1,3-雙酮、萘醇、Feist-Bénary
英文關鍵詞：	allylic acetates, tetrasubstituted furans, naphthofurans, 1,3-diketones, naphthol, Feist-Bénary
論文種類：	學術論文
相關次數：	點閱：77 下載：2
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合成多取代呋喃與呋喃衍生物為有機合成中具挑戰性及重要的一環，本文以丙烯基醋酸酯為前驅物，分別與容易取得的1,3-雙酮/α-拉電子取代基酮類起始物，經過一系列條件篩選及取代基探討，推測反應機構經由SN2’ 加成－脫去反應，進行Feist-Bénary type反應，合成高產率之四取代呋喃產物（up to 99%）。其中，以1,3-環戊酮為起始物，則得到吡喃為主產物。另一方面，若以萘醇為起始物，不需路易士酸催化，即進行Freidel-Crafts SN2'反應過程，接著，以oxa-Micheal 合環反應，有效合成萘併呋喃（up to 96%）。此方法能應用於丙烯基醋酸酯上，含有各種拉電子基、推電子基、雜環取代及烷基取代。然而，欲合成苯併吲哚並未得到預期結果，得到SN2反應而未環化的產物。

Synthesis of polysubstituted furans and naphthofurans represent an important subclass in organic synthesis. Herein, we develop a new synthetic strategy for accessing tetrasubstituted furans by Feist-Bénary type reaction between allylic acetate precursor and 1,3-dicarbonyl/ α-withdrawing ketones. After studying a series of substrate scope under optimized conditions, we provided a reasonable mechanism. In this process, nucleophile attacks to Michael acceptor by SN2’ process, then undergo addition-elimination to give desired aromatic furan compounds（chemical yield up to 96% ）. The use of 1,3-cyclopentandione as starting material, pyran is obtained as major product. On the other hand, use of naphthol as starting material, reaction proceeded through Freidel-Crafts SN2' process followed by intramolecular oxa-Micheal cyclization and subsequently aromatization to give naphthofurans（chemical yield up to 96%）. This method can be applied to different functional groups on allylic acetates, such as electron-donating, electron-withdrawing, heteroaromatic and aliphatic groups. However, when 1-aminonaphthalene was used as the nucleophile, instead of the desired benzoindole, we got SN2 addition compound.

中文摘要....................................................4
英文摘要....................................................5
第一章    緒論
1-1呋喃的背景與應用………………………………………………………………...................6
1-2萘並呋喃的應用…………………………………………………………………...................8
1-3呋喃相關文獻介紹………………………………………………………………..................9
  1-3-1直接對呋喃進行官能基化反應……………………………………………............10
  1-3-2 非環狀系統進行環化反應………………………………………………..............11
    1-3-2-1 Paal-Knorr 反應………………………………………………………..........11
    1-3-2-2 Feist-Bénary 反應…………………………………………………..........12
    1-3-2-3 有機膦試劑環化縮合反應……………………………………………...........14
    1-3-2-4 過渡金屬催化合成呋喃分子…………………………………………..........17
      1-3-2-4-1 聯烯類化合物之環化反應……………………………………….........17
      1-3-2-4-2 α-炔基烯酮之環化反應………………………………………….........18
      1-3-2-4-3環丙烯基烯酮之環化反應………………………………………..........20
1-4萘並呋喃相關文獻介紹…………………………………………………………................22
  1-4-1 鋰試劑合成萘並呋喃……………………………………………………...............22
  1-4-2 氧化鋁合成萘並呋喃……………………………………………………...............23
  1-4-3 過渡金屬合成萘並呋喃…………………………………………………..............25
1-5研究動機…………………………………………………………………………....................27

第二章 結果與討論
2-1 起始物丙烯基醋酸酯之製備…………………………………………………..............28
2-2 合成多取代呋喃反應之探討………………………………………………….............29
  2-2-1鹼試劑之篩選…………………………………………………....................30
  2-2-2溶劑效應………………………………………………….........................31
  2-2-3 1,3-環狀雙酮始物與丙烯基醋酸酯反應之探討……….............32
  2-2-4 環戊二酮與丙烯基醋酸酯反應生成吡喃反應之探討………..........35
  2-2-5 α-拉電子取代基酮類起始物合成四取代呋喃………...............36
2-3 合成呋喃反應機構之探討……….................................38
2-4 Friedel-Crafts反應合成萘併呋喃之探討………...................39
  2-4-1優化條件篩選………......................................39
  2-4-2不同起始物之探討….....................................41
2-5 萘胺與丙烯基醋酸酯反應之探討…..............................43
2-6 合成萘併呋喃反應機構之探討…...............................45
2-7 結論………...............................................46

第三章 參考文獻.............................................47

                                

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