臺灣博碩士論文加值系統

本篇論文旨在以鈀金屬催化異相耦合反應，用Kumada Reaction合成2-聯苯-4,6-二(12-苯基吲哚駢[2,3-a]咔唑)-1,3,5-三氮代苯 (51) 以及用Suzuki Reaction合成雙苯駢環庚萘環衍生物 (42、58)。
合成化合物 51 的過程中，我們利用與原作者不同的合成路徑，以更方便、快速且安全的合成方法來拿到目標產物，因此排除了原作者的合成路徑中，化合物 49 可能不穩定存在的疑慮並探討其晶體結構性質。
在合成並測試雙苯駢環庚萘環衍生物的反應中，發現鈀金屬催化劑、鹼、溶劑、溫度均扮演關鍵的角色。合成8,9,12,13-四甲基雙苯駢[4,5:6,7]環庚[1,2,3-de]萘環化合物 (42)，已知的最佳反應條件為將2,2'-雙碘聯苯 38、1,8-二硼酸酐萘 41、三(二苯乙烯基丙酮)二鈀(0)以及磷酸三鉀溶在甲苯、乙醇和水的混合溶液中，再加熱至120 oC，產率82%。而在合成8,9,12,13-四甲氧基雙苯駢[4,5:6,7]環庚[1,2,3-de]萘環化合物 (58)，已知的最佳反應條件為將2,2'-雙碘聯苯 56、1,8-二硼酸酐萘 41、三(二苯乙烯基丙酮)二鈀(0)以及磷酸三鉀溶在乙腈和水的混合溶液中，再加熱至40 oC，產率66%。

The main goal of this thesis is to synthesize 2-biphenyl-4,6-bis(12-phen-
ylindo[2,3-a]carbazole)-1,3,5-triazine (51) via Kumada Reaction and dibenzocycloheptanaphthalene derivatives (42、58) via Suzuki Reaction.
In the synthetic process of compound 51, we get the final compound using faster, safer and more convenient method different from the original one. We also remove the doubts about compound 49 may decompose and investigate its crystal structure properties.
Systematic studies of the dibenzocycloheptanaphthalene derivatives reaction conditions revealed that palladium catalyst, base, solvent and temperature all play key roles. In the synthetic procedure of 8,9,12,13-tetramethyldibenzo[4,5:6,7]cyclohepta[1,2,3-de]naphthalene (42), the reaction conditions have been optimized. Upon heating 2,2'-diiodobiphenyl (38) and 1,8-naphthalenediyldiboric acid anhydride (41) in the solution of toluene, ethanol and water at 120 oC with a mixture of Pd2(dba)3, K3PO4 can be obtained in 82% yield. And in the synthetic procedure of 8,9,12,13-tetramethoxydibenzo[4,5:6,7]cyclohepta[1,2,3-de]nap-
hthalene (19), the reaction conditions have also been optimized. Upon heating 2,2'-diiodobiphenyl (56) and 1,8-naphthalenediyldiboric acid anhydride (41) in the solution of acetonitrile and water at 40 oC with a mixture of Pd2(dba)3, K3PO4 can be obtained in 66% yield.

中文摘要..................................................III
英文摘要...................................................IV
誌謝.......................................................V
表目錄...................................................VIII
圖目錄...................................................IX
壹、 緒論
一、前言................................................1
二、OLED材料分子.........................................4
三、七圓環化合物..........................................6
貳、 結果與討論
一、2-聯苯-4,6-二(12-苯基吲哚駢[2,3-a]咔唑)-1,3,5-三氮代苯
(一)、合成2-聯苯-4,6-二(12-苯基吲哚駢[2,3-a]咔唑)-1,3,5-
三氮代苯.....................................11
(二)、結構的解析....................................13
二、四甲基雙苯駢環庚萘環化合物
(一) 合成四甲基雙苯駢環庚萘環化合物.....................14
(二) 鈀催化劑的影響..................................14
(三) 溫度的影響.....................................16
(四) 鹼的影響......................................17
(五) 溶劑的影響.....................................18
(六) 反應最佳化.....................................19
(七)、結構的解析....................................20
三、四甲氧基雙苯駢環庚萘環化合物
(一) 合成四甲氧基雙苯駢環庚萘環化合物...................21
(二) 溶劑的影響.....................................22
(三) 鈀催化劑的影響..................................23
(四) 鹼的影響......................................24
(五) 溫度的影響.....................................25
(六) 反應最佳化.....................................26
參、 結論..............................................27
肆、 實驗..............................................28
伍、 參考文獻...............................................38
陸、 附錄
一、核磁共振光譜圖.......................................41
二、X-ray單晶繞射分析資料................................47

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