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姓名	張善芸(Shan-Yun Chang)  查詢紙本館藏	畢業系所	化學工程與材料工程學系
論文名稱	噻吩并[3,4-c]吡咯-4, 6-二酮(TPD)之鈀催化直接碳氫鍵芳香環化反應之研究: 以高步驟經濟效益合成策略製備含TPD之功能性π-共軛小分子 (Pd-Catalyzed Direct C-H Arylation of Thieno[3,4-c]pyrrole- 4,6-dione (TPD): A Step-Economical Synthetic Alternative to Access Symmetrical π-Conjugated Functional Molecules)
相關論文	★ 人類胚胎幹細胞在無滋養層及無異種條件的培養下於帶有生長因子的表面進行培養 ★ 鈣鈦礦膜缺陷控制及製備高效率鈣鈦礦太陽能電池 ★ 銅觸媒催化之直接碳氫鍵芳香環化反應：以高效率低成本之新合成策略製備含噻吩并[3,4-c]吡咯-4, 6 -二酮(TPD)之功能性有機材料 ★ 芳香雜環碘化物之水相自身耦合反應：有機光電材料重要前驅物之綠色化學合成法之研究 ★ 鈷觸媒催化之芳香雜環溴化物還原性烷基化反應： 以一鍋化反應製備烷基噻吩、呋喃、硒吩與吡咯之有機光電材料重要前驅物 ★ 利用碳氫鍵芳香環化反應高效率合成小分子有機半導體材料之末端基與其在染料敏化太陽能電池之應用 ★ 銅催化之碳氫鍵芳香環化反應於染料敏化太陽能電池之綠色合成與應用 ★ 利用交叉脫氫耦合反應快速製備各式D-π-A有機染料分子：C-H/C-H合成法研究與其在染料敏化太陽能電池之應用 ★ 鈀催化之碳氫鍵活化反應： 發展省步驟且具位向選擇性新合成途徑 快速製備有機光電材料重要之π-A-π結構 ★ 發展功能性π共軛小分子之綠色合成方法學及其於太陽能電池之應用 ★ 利用碳氫鍵芳香環化反應一步合成含EDOT電洞傳輸材料及其於鈣鈦礦太陽能電池之應用 ★ 碳氫鍵活化反應於鈣鈦礦太陽能電池之應用：高效能電洞傳輸材料合成捷徑之研究 ★ 結合C-H/C-Br與C-H/C-H反應快速合成快速合成有機光敏化劑並探討內部拉電子基對於有機光敏化劑並探討內部拉電子基對於 有機光敏化劑並探討內部拉電子基對於 有機光敏化劑並探討內部拉電子基對於 有機光敏化劑並探討內部拉電子基對於 有機光敏化劑並探討內部拉電子基對於染料敏化太陽能電池效率之染料敏化太陽能電池效率之染料敏化太陽能電池效率之染料敏化太陽能電池效率之影響 ★ 一鍋化連續式碳氫鍵芳香環化反應於染料敏化太陽能電池與鈣鈦礦太陽能電池之應用 ★ 利用反應條件最佳化之碳-氫/碳-溴合成策略快速製備以并三?吩為核心結構之電洞傳輸材料 ★ 含?唑與吩??之電洞傳輸材料於鈣鈦礦太陽能電池之應用：發展碳氫鍵芳香環化之省步驟合成法
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摘要(中)	以thieno[3,4-c]pyrrole-4,6-dione (TPD)為核心作分子共軛延伸的結構已在光電元件上被廣泛研究，在本論文中，探討以鈀催化直接碳氫鍵活化之方法取代傳統的交叉耦合反應來製備含TPD單元的π共軛功能性小分子。碳氫鍵活化的方法不僅具有步驟經濟性、原子經濟性、減少副產物產生，成本低於傳統的交叉耦合反應，故鈀催化之直接碳氫鍵活化之合成方法已逐漸取代傳統交叉耦合反應。 本研究一開始以TPD與溴苯為反應物，嘗試不同的催化劑、配位基、鹼、溶劑，以找到最佳化條件，其中，我們發現溶劑的極性對於反應的轉換率具有決定性的影響。利用找到的最佳化條件，TPD或其衍生物與具有各種不同官能基的芳香基溴化物可順利地進行鈀催化碳氫鍵活化的反應。此反應中對於官能基容忍性非常好，像是酯基、腈基、酮基、醛基還有含鹵素基都是可以被容忍的。
摘要(英)	We demonstrate a step-economical and viable synthetic alternative to access a series of thieno[3,4-c]pyrrole-4,6-dione (TPD)-based π-conjugated molecules through Pd-catalyzed direct C-H arylations. A comprehensive synthetic study including the screening of various kinds of palladium catalysts, ligands, and bases is reported. Under the optimum reaction conditions, TPD and its common derivatives underwent efficient and mild direct C-H arylations with a variety of functionalized bromoarenes. Functional groups such as ester, nitrile, ketone, aldehyde, and halide were well-tolerated, which substantially extended the reaction scope. We wish the reported method would provide materials scientists a relatively greener synthetic route to efficiently prepare the TPD-containing π-functional materials.
關鍵字(中)	★ 噻吩并[3,4-c]吡咯-4, 6-二酮 ★ 鈀催化直接碳氫鍵芳香環化反應 ★ 高步驟經濟效益 ★ 功能性π-共軛小分子	關鍵字(英)	★ Thieno[3,4-c]pyrrole- 4,6-dione ★ Pd-Catalyzed Direct C-H Arylation ★ Step-Economical ★ π-Conjugated Functional Molecules
論文目次	目錄 中文摘要…………………………………………………………………….i 英文摘要…………………………………………………………………….ii 致謝............................................................................................................iii 目錄………………………………………………………………………….iv 圖目錄………………………………………………………………………..vi 表目錄……………………………………………………………………….vii 中英對照表………………………………………………………………….viii 一、緒論…………………………………………………………………….1 1-1 過渡金屬催化之碳氫鍵活化耦合反應…………………………..1 1-2 π共軛功能性分子……………………………………………….4 1-3 含TPD結構之功能性分子合成法概述………………………….7 二、實驗部分………………………………………………………………..15 2-1 尋找反應最佳化條件……………………………………………...15 2-2 探討不同的芳香基溴化物與TPD之交叉耦合反應……………..25 2-3 以最佳化條件合成A’-π-A-π-A’功能性分子…………………..…33 2-4 反應機制…………………………………………………………...36 三、結論與展望……………………………………………………………..39 四、儀器設備與藥品溶劑…………………………………………………..40 4-1 儀器設備…………………………………………………………...40 4-2 藥品與溶劑………………………………………………………...41 五、合成步驟與化合物鑑定…………………………………………..……...42 參考資料……………………………………………………………………...75 NMR圖譜…………………………………………………………………….83
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指導教授	劉青原(Ching-Yuan Liu)	審核日期	2014-7-21
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