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研究生:蔡承軒
研究生(外文):Tsai Chen Hsuan
論文名稱:應用多組成反應合成色烯類及其他雜環化合物
指導教授:姚清發姚清發引用關係
指導教授(外文):Yao, Ching-Fa
學位類別:碩士
校院名稱:國立臺灣師範大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
畢業學年度:97
語文別:中文
論文頁數:241
中文關鍵詞:四丁基氟化銨多組成反應色烯類化合物
外文關鍵詞:TBAFmulticomponentchromene
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本實驗以「理想合成(ideal synthesis)」及「綠色化學(green chemistry)」為目標,開發出快速、高產率的合成方法,並結合多組成反應策略(multicomponent strategy)及氟化四丁基銨(Tetrabutylammonium fluoride, TBAF.3H2O),在水溶液中迴流,合成一系列色烯類衍生物及其他雜環化合物,反應中經過Knoevenagel縮合及環化加成反應兩步驟,其中不需任何純化即可得到最終產物;利用產物不溶水的特性,過濾回收含有氟化四丁基銨的水溶液便可再次催化反應進行,此為本實驗最大的發現與收獲。
The main theme of the dissertation is to study the multicomponent reactions (MCRs). The investigations carried out were divided into four chapters.
The first chapter includes the synthesis of chromene which was obtained by the condensation of an aromatic aldehyde, malononitrile and demidone catalyzed by reusable catalyst TBAF.
The second chapter includes the reaction of aromatic aldehyde, β-napthol and dimidone to afford xanthenone derivative in good yields.
The third chapter describes the synthesis of benzochromene achieved from the MCR of aromatic aldehyde, malononitrile and α- or β-napthol.
The fourth chapter illustrates the synthesis of aromatic aldehyde, malononitrile and α- or β-napthol to the corresponding benzopyranopyridine.
The generality of the above MCRs were studied with a variety of aromatic aldehydes including electron-donating and electron-withdrawing groups and found to be equally good. The use of water as the solvent and also the recyclability of the catalyst (TBAF) employed has the advantages of being economically viable and more efficient for the multicomponent reactions in aqueous media. Overall we can have developed simple and efficient routes for the synthesis of biologically important heterocycles.
中文摘要..................................................................................................I
Abstract II
縮寫對照表 III
目錄 III
壹、緒論 1
1.1前言 1
圖一、Efavirenz與Sarin之結構 1
表一、商業上常用氟化物及其優缺點 3
1.2氟化物在有機合成上的應用 3
1.2.1 親核基取代反應(Nucleophilic substitution) 4
1.2.2 脫去反應(Elimination) 5
圖二、4-Bromocholest-4-en-3-one之結構 6
1.2.3 加成反應(Addition) 7
圖三、羅賓遜成環反應 9
1.3 多組成反應(multicomponent reaction)的發展與應用 11
表二、多組成反應的類型 13
1.4色烯類衍生物(chromene)的簡介 17
圖四、2H-色烯、4H-色烯與異色烯的結構 17
圖五、七葉內酯、蛇床子素與亮菌甲素 18
圖六、雙香豆素、華法林與醋硝香豆素 19
圖七、Pechmann condensation之反應機構 20
圖八、色酮、黃酮與醋異黃酮 21
圖九、黃芩苷、葛根素與醋白果素 21
貳、實驗結果與討論 22
2.1 在水溶液中利用氟離子催化多組成反應策略有效的合成色烯及喹啉類衍生物 22
表三、催化劑對反應的影響a 24
表四、氟離子催化一鍋式合成色烯和喹啉衍生物a 26
表五、氟離子催化一鍋式合成spirochromene及其衍生物a 28
2.2 在簡單且環保的反應條件下利用氟化四丁基銨製備tetrahydrobenzo[a]xanthen-11-one derivatives 30
圖十、黃嘌呤素與玫瑰紅等染料結構 31
圖十一、黃嘌呤酮、Mangostin和芒果苷結構 32
圖十二、理想合成的定義 33
表六、添加物在一鍋式合成benzo[a]xanthen衍生物之影響 33
表七、重覆使用回收的氟化四丁基銨催化反應a 36
表八、氟化四丁基銨催化合成benzo[a]xanthen及衍生物 37
2.3 利用傳統或微波加熱及氟化四丁基銨,在水溶液中快速的合成2-Amino-3-cyano-4-phenyl-4H-benzochromene 40
表九、各式溶劑的tan δ值(2.54GHz, 20℃) 42
表十、添加物在一鍋式合成benzo[a] chromene衍生物之影響a 44
表十一、溶劑在一鍋式合成benzo[a] chromene衍生物之影響a 45
表十二、氟化四丁基銨催化合成benzo[a] chromene衍生物a 46
表十三、重覆使用回收的氟化四丁基銨催化反應a 50
2.4氟離子催化一鍋式反應快速合成benzopyranpyridine 50
圖十三、具生物活性之benzopyranopyridine衍生物 51
表十四、多取代benzopyranopyridine之衍生物合成a 52
2.5結論 53
参、實驗部分 54
3.1 一般實驗方法 54
3.2 藥品與試劑 56
3.3實驗程序與光譜資料 57
肆、參考文獻 95
伍、1H與13C光譜附圖 100
陸、論文發表與獎項 241
肆、參考文獻
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45. 本論文大部分與高士杰博士合作並共享其成果。
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