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論文名稱 Title |
利用二價汞化合物催化環化反應合成3-醯基苯并[b]噻吩之研究 Synthesis of 3-Acylbenzo[b]thiophenes via Mercury (II)-Catalyzed Cyclization reaction |
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系所名稱 Department |
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畢業學年期 Year, semester |
語文別 Language |
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學位類別 Degree |
頁數 Number of pages |
191 |
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研究生 Author |
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指導教授 Advisor |
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召集委員 Convenor |
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口試委員 Advisory Committee |
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口試日期 Date of Exam |
2011-06-13 |
繳交日期 Date of Submission |
2011-07-20 |
關鍵字 Keywords |
苯并噻吩、二價汞化物、Pummerer type 環化反應、亞碸 mercury dichloride, benzo[b]thiophene, sulfoxide, Pummerer type cyclization reaction |
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統計 Statistics |
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中文摘要 |
本論文研究以鄰位具炔類取代基之亞碸化合物,經二價汞化物催化反應,以苯為溶媒,加熱迴流反應24 小時,得到三號位置具醯基取代基之苯并噻吩化合物。比較炔類結構上具不同取代基之亞碸反應物,則取代基為推電子基者,所得之苯并噻吩產率較高;拉電子基取代基 則降低苯并噻吩之產率。其它亞碸反應物,以benzyl 取代原本硫原子所具有之甲基取代基,則增進反應之產率。同位素效應之研究,發現該反應途徑為Pummerer type 環化反應。 |
Abstract |
Treatment of 1-(methylsulfinyl)-2-(phenylethynyl)benzene with 10 mol % of mercury dichloride and 1 equivalent of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in refluxing benzene gave benzo[b]thiophene in good yields. This method tolerated various functional groups in phenylethynyl moiety, including electron donating groups and electron withdrawing groups. Useing 1-(benzylsulfinyl)-2-(phenylethynyl)benzene as reaction substrate increased the yields of benzo[b]thiophene derivatives. Isotope effect showed that this cyclization reaction belong to Pummerer type cyclization reaction. |
目次 Table of Contents |
中文摘要.......................................................................................................ii Abstract ........................................................................................................iii 圖目錄..........................................................................................................vi 表目錄.........................................................................................................vii 第一節 緒論................................................................................................. 1 1.1 苯并噻吩的介紹............................................................................. 1 1.2 二、三號位有取代基的苯並噻吩合成......................................... 5 1.3 近十年苯并噻吩一步驟的合成反應............................................. 9 (I) 自由基環化反應....................................................................... 9 (II) 親電性金金屬合成................................................................ 10 (III) Pummerer type 的環化反應................................................. 10 1.4 金化物催化之缺類加成反應....................................................... 12 1.4.1 前言..................................................................................... 12 1.4.2 Hydroamination of alkyne.................................................... 12 1.4.3 Hydroalkoxylation of alkyne................................................ 12 1.4.4 Cyclization of b-ynones........................................................ 13 1.4.5 以sulfoxide 當作nucleophile ............................................ 13 第二節 結果與討論................................................................................... 16 2.1 研究動機....................................................................................... 16 v 2.2 起始物製備................................................................................... 17 2.3 最佳化條件之尋找....................................................................... 20 2.4 3-Acylbenzothiophenes 之合成..................................................... 27 2.5 同位素氘取代探討反應機構....................................................... 29 第三節 結論............................................................................................... 31 第四節 參考文獻....................................................................................... 32 第五節 實驗部份....................................................................................... 35 5.1 儀器部分....................................................................................... 35 5.2 藥品............................................................................................... 36 5.3 實驗步驟....................................................................................... 38 光譜資料...................................................................................................................... 74 |
參考文獻 References |
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