臺灣博碩士論文加值系統

具有黃酮類化合物(flavonoid)與類黃酮(flavanone)結構為主幹的分子存在於自然界的植物或水果中，隨著官能基的不同和位置的差異分別具有不同的生物活性及製藥潛能，例如：抗氧化、抗發炎、抗菌、抗癌…等。本篇論文致力於研究並合成屬於類黃酮(flavanone)衍生物。其合成法是利用本實驗室所開發的陽離子配位基和醋酸鈀形成的催化系統以色酮與芳基苯硼酸在水中進行共軛加成反應，透過此催化系統可以合成出擁有不同官能基的類黃酮衍生物。相較於其他論文探討的合成方式和條件，本研究降低了觸媒的使用量並達到極佳的選擇性和良好的產率；除此之外，使用水當唯一溶劑，萃取後的觸媒水溶液還可進行數次再使用的實驗。

Flavonoids and flavanones are privileged structural motifs in numerous nature products and pharmaceutical molecules that show a variety of biological activities. For example: anti-oxidation, anti-inflammatory, anti-bacterial, anti-cancer and so on. In this study, we developed a Pd(OAc)2/cationic 2,2’-bipyridyl-catalytic system to catalyzed conjugate addition of chromones and arylboronic acids forming flavanone derivatives using water as the reaction medium. In comparison with other published conditions, our reaction not only use water as the green solvent for the further reuse studies but achieve excellent selectivity and good to excellent yields under low catalyst loading.

摘要 i
ABSTRACT ii
謝誌 iii
目錄 iv
表目錄 vi
圖目錄 vii
第一章 緒論 1
1.1 前言 1
1.2 Flavanone衍生物之功用簡介 2
1.3 綠色溶劑 8
1.4 親水性配位基 9
1.4.1 親水性Nitrogen配位基介紹 10
1.5 Conjugate addition之相關反應介紹 12
1.5.1 金屬觸媒催化有機硼試劑進行conjugate addition反應 14
1.6 Flavanone衍生物之合成相關反應文獻介紹 18
1.7 研究動機 23
第二章 實驗部分 25
2.1 實驗儀器 25
2.1.1 氣相層析儀 (Gas Chromatography, GC) 25
2.1.2 核磁共振光譜儀(Nuclear Magnetic Resonance Spectroscopy, NMR) 25
2.2 實驗藥品 26
2.3 試劑純化 26
2.4 實驗過程 26
2.5合成Cationic 2,2’-bipyridyl ligand與光譜數據 27
2.6 實驗步驟與光譜數據 32
2.6.1 起始物芳基香基色酮之合成步驟與光譜數據 32
2.6.2 類黃酮衍生物之耦合反應實驗步驟及光譜數據 35
2.6.3 Pd(OAc)2/L水溶液再使用之實驗步驟 66
2.6.4 利用DDQ/NaNO2氧化合成黃酮衍生物(Flavone) 67
第三章 結果與討論 68
3.1 芳基色酮與芳基苯硼酸之共軛加成反應結果與討論 68
3.1.1 類黃酮衍生物合成之最適化條件探討 68
3.1.2 5,7-Dimethoxyflavanone衍生物之結果與討論 70
3.1.3 6-Methoxyflavanone衍生物之結果與討論 74
3.1.4 7-Methoxyflavanone衍生物之結果與討論 78
3.1.5 7-Fluoroflavanone衍生物之結果與討論 82
3.1.6 芳基色酮與芳基苯硼酸反應結果之比較 86
3.2 鈀觸媒水溶液再使用之結果與討論 89
3.3利用DDQ/NaNO2氧化合成黃酮Flavone衍生物之結果與討論 91
3.4 反應機構 94
第四章 結論 96
參考文獻 97
附錄：Flavanone衍生物之1H及13C NMR光譜圖 103

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