臺灣博碩士論文加值系統

具有多酚官能基且以反式二苯乙烯 (stilbenes) 為主體的化合物，都可能有生物活性或抗氧化的功效，以白藜蘆醇 (resveratrol) 為例，其為多酚類抗氧化素，主要存在於葡萄、野果、花生等果實中，是植物所分泌的抗病毒素，可以用來預防炎症，心臟疾病，老化，癌症等等，此外，它有自由基清除活性，可以有神經保護作用，抗病毒活性，抗氧化劑，脂質修飾等功能。在這類型的天然物提取上十分困難，需要大量的新鮮葡萄果皮才能提取出少許的白藜蘆醇，且僅能得到單一種類的多酚化合物，我們若找到簡易的合成方式，就能大量取得具生物活性的白藜蘆醇及各種不同官能基的多酚類衍生物。
於是，我們利用實驗室自行合成的陽離子水溶性配位基結合PdCl2(NH3)2，在水相中，成功合成出甲氧基在不同位置的反式二苯乙烯衍生物。本實驗以純水為溶劑在空氣下，利用tetrabutylammonium bromide (TBAB) 作為反應系統裡的界面活性劑，可成功地讓苯乙烯衍生物與芳香性鹵化物進行Mizoroki-Heck反應，且萃取後殘留的鈀觸媒水溶液可以進行再使用達3次以上。

Trans-stilbenes with polyphenolic functional groups may have biological activity and antioxidant effect. Taking resveratrol as an example, it is a polyphenol antioxidant, has been found in various food sources such as grapes, berries, and peanuts. It is a phytoalexin and can be applied to the prevention of inflammation, heart disease, aging, etc. It is very difficult to extract this type of natural product. Because a large amount of grape peel is needed to extract a little resveratrol, and only a single type of polyphenol compound can be obtained. We have found a simple method of synthesis, can be achieved with a large number of biologically active resveratrol and functional groups of various polyphenolic derivatives.
Therefore, we have recently prepared a water-soluble cationic 2,2’-bipyridyl ligand and utilized it to bring a PdCl2(NH3)2. In the aqueous phase, we successfully synthesized trans-stilbene derivatives with different methoxy groups at diverse positions. In this experiment, tetrabutylammonium bromide was used as a phase-transfer agent in the reaction system using pure water as the solvent, and the styrene derivatives and the aromatic halides were successfully subjected to the Mizoroki-Heck reaction. After extraction, the residual aqueous solution could be reused several times with only a slight decrease in its activity.

中文摘要 i
英文摘要 ii
目 錄 iv
謝 誌 iii
表目錄 vii
圖目錄 viii
第一章 緒論 1
1.1 前言 1
1.2 關於白藜蘆醇及衍生物之介紹 2
1.3 關於白藜蘆醇反應之相關研究 7
1.3.1 探討有機方法製備trans-stilbene 7
1.3.1.1 Wittig反應 7
1.3.1.2 Horner-Wadsworth-Emmons (HWE) 反應 9
1.3.1.3 Perkin縮合反應 9
1.3.2 探討過渡金屬催化合成trans-stilbene 10
1.3.2.1 在水中進行Mizoroki-Heck反應 10
1.3.2.2 以Mizoroki-Heck反應合成白藜蘆醇 13
1.3.2.3 一步合成白藜蘆醇 17
1.4 研究動機 18
第二章 實驗部分 19
2.1 實驗儀器 19
2.1.1 氣相層析儀 (Gas chromatography, GC) 19
2.1.2 核磁共振光譜儀 (Nuclear magnetic resonance spectroscopy, NMR) 19
2.1.3 高解析度質譜儀 20
2.1.4 熔點觀測儀 (Melting point apparatus) 20
2.2 實驗藥品 20
2.3 試劑純化及除水乾燥 20
2.4 實驗過程 21
2.5 水溶性cationic 2,2-bipyridyl ligand之合成與光譜 22
2.6 起始物之合成步驟與光譜數據 26
2.6.1 合成styrenes起始物與光譜數據 26
2.6.2 合成1-iodo-3,4-dimethoxybenzene起始物與光譜數據 28
2.6.2 合成aryl iodides起始物與光譜數據 29
2.6.3 合成1-iodo-3,5-dihydoxybenzene起始物與光譜數據 30
2.6.4 合成5-iodo-2-methoxyphenol起始物與光譜數據 32
2.7 實驗步驟與光譜數據 34
2.7.1 鈀觸媒催化aryl iodides和styrenes行Mizoroki-Heck反應之實驗步驟與光譜數據 34
2.7.2 鈀觸媒催化aryl halides和styrenes行Mizoroki-Heck反應之實驗步驟與光譜數據 45
2.7.3 甲氧基取代二苯乙烯進行demethylation 52
第三章 結果與討論 54
3.1 鈀觸媒催化進行Mizoroki-Heck反應之結果與討論 54
3.1.1 Aryl iodides和styrenes行Mizoroki-Heck反應之最適化條件探討 54
3.1.2 Aryl iodides和styrenes在水相進行Mizoroki-Heck反應之結果與討論 58
3.1.3 Aryl halides和styrenes在水相進行Mizoroki-Heck反應之結果與討論 61
3.1.4 水溶液鈀觸媒系統再使用之結果與討論 63
3.1.5 以BBr3進行去甲基得到天然物白藜蘆醇 65
3.1.6 反應機構探討 66
第四章 結論 67
參考文獻 68
附錄 74

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