臺灣博碩士論文加值系統

1,2,3-三嗪(5)被視為缺電子的含三氮六員雜環化合物，由於其化學性質不穩定並且製備合成不易，是所有三嗪類化合物家族中最晚被研究的，相關研究文獻並不多。近期探討1,2,3-三嗪(5)反應活性的研究有逐步發展的趨勢，例如在1,2,3-三嗪(5)的4、5、6號位置引入推電子基或是拉電子官能基進行修飾，再透過逆向狄耳士–阿爾德反應來進行環加成反應，或者利用親核試劑在C4或C5位置進行親核加成反應。在本篇論文中，我們以乙腈作為溶劑，使用二級胺與1,2,3-三嗪(5)進行親核加成反應，反應過程時會脫去一分子氮氣，形成亞胺中間體，搭配二價醋酸銅與氧氣的反應條件，將亞胺中間體進一步氧化形成trans-β-acrylonitriles產物。優化後的反應條件在不同種類的二級胺與1,2,3-三嗪(5)進行親核加成氧化反應皆有不錯的產率。而在後續的實驗中我們也發現了反應在含水條件下可能對亞胺中間體進行水解導致產率降低，我們也將氧氣換成氮氣後觀察氧氣對銅離子進行氧化反應的影響。而這個好氧銅催化反應也幫助我們拓展1,2,3-三嗪在有機化學中的應用性。

Triazines are three nitrogen atoms-containing six-membered ring compounds. The isomers of triazines can be distinguished from each other by the positions of their nitrogen atoms, which are referred to as 1,2,3-triazines, 1,2,4-triazines, and 1,3,5-triazines, respectively. 1,2,3-Triazines are classified as electron-deficient heterocycles that are the least investigated because their ring system is considered to be the least stable and their synthetic routes are limited. Recent, several studies have demonstrated the reactivity of selected 1,2,3-triazines to participate in inverse electron demand Diels-Alder reactions with various amine-related dienophiles. In this thesis, we present a user-friendly and effective synthesis of trans-β-acrylonitriles based on the oxidative nucleophilic addition of secondary amines to 1,2,3-triazine (5). The addition of secondary amines, including cyclic amines and heterocyclic amines as well as asymmetric amines, to 1,2,3-triazine (5) under mild reaction conditions (CH3CN, 25‒60 oC, 3‒60 h) by oxidation of Cu(II) species with using O2 to fulfill the promoted cycle. The reaction proceeds by amine nucleophilic addition to C-4 of the 1,2,3-triazine core with highly regioselectivity, in situ loss of nitrogen, and subsequent imine oxidation to generate trans-β-acrylonitriles. Further studies on the scope and synthetic applications of this reaction are currently underway.

摘要 i
ABSTRACT ii
誌謝 iii
目錄 iv
圖目錄 vi
表目錄 viii
縮寫表 ix
第一章 緒論 1
1-1 前言 1
1-2 雜環化合物 2
1-3 1,2,3-三嗪之相關研究 5
1-3-1 1,2,3-三嗪的環加成反應 5
1-3-2 1,2,3-三嗪的親核反應 15
1-4 高價碘化合物 17
1-5 有氧銅催化反應 18
1-5-1 烯烴的好氧銅催化 19
1-5-2 炔胺的好氧銅催化 21
第二章 實驗結果與討論 23
2-1 起始物1,2,3-三嗪的合成 23
2-2 高價碘試劑氧化1,2,3-三嗪反應 23
2-2-1 高價碘試劑氧化1,2,3-三嗪反應之溶劑篩選 24
2-2-2 高價碘試劑氧化1,2,3-三嗪反應之氧化劑篩選 25
2-3 好氧銅促進反應 27
2-3-1 溶劑之篩選 28
2-3-2 促進劑當量數之篩選 29
2-3-3 促進劑之篩選 30
2-3-4 控制實驗 32
2-4 優化條件 34
2-5 反應物範圍測試 35
2-6 反應機制討論 40
第三章 結論 42
第四章 實驗部分 43
4-1 實驗儀器 43
4-1-1 核磁共振光譜儀(Nuclear Magnetic Resonance Spectroscopy, NMR) 43
4-1-2 高解析質譜儀 43
4-1-3 FTIR近紅外光譜儀 44
4-1-4 熔點測定儀 44
4-1-5 減壓式迴旋濃縮儀 44
4-2 實驗藥品 44
4-3 TLC薄層色層分析 44
4-4 合成步驟 45
參考文獻 57
附錄 61

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