臺灣博碩士論文加值系統

本實驗室劉志奮所合成的 anthraquinone肟酯化合物在光引導下具有良好的切割DNA效果，尤其是以 para 位置接 CN, NO2, F 的衍生物有最好的切割效果，可切雙股DNA。本論文則以 anthraquinone 和fluorenone為主體，並在環上增加二個氮原子，所合成的含氮環的肟酯化合物，期望能得到更好的切割效果。
首先由化合物2、5分別合成肟化合物3和6，再利用氫化鈉拔除其羥基質子，再與不同對位取代的苯甲醯氯衍生物進行親核性取代反應，共合成8個肟酯化合物4a－4d、7a－7d，並由中央大學胡紀如教授實驗室測試其切割DNA之效能。
本論文亦探討肟酯化合物4a於氮氣下，在苯中之光解產物及反應機構。由實驗之結果推測肟酯化合物4a於紫外光照射下，其鍵能較弱之氮-氧鍵會均解，形成亞胺自由基及苯甲酸根自由基。亞胺自由基可獲得兩個氫原子而形成不穩定之亞胺化合物8，進而水解成化合物2；而苯甲酸根自由基則捕捉氫原子形成苯甲酸 (9)。

Abstract
Our laboratory reported earlier that anthraquinone oxime esters have good photo-induced DNA-cleaving efficiency. This thesis describes the synthesis of eight more oxime esters derived from anthraquinone and fluorenone skeletons which have two nitrogen atoms on the ring with the hope of getting better DNA-cleaving results.
Deprotonation of oximes 3 and 6 with sodium hydride followed by treatment with para-substituted benzoyl chlorides (p-YC6H4COCl; Y=H, CH3, F, CN) gave the oxime esters 4a－4d and 7a－7d which have been tested for their DNA-cleaving efficiency by Professor J. R. Hwu’s laboratory in National Central University.
The second part of the thesis studies the photocleavage of oxime ester 4a in benzene under nitrogen to give diketone 2 and benzoic acid (9). From the products obtained it was proposed that the weak N-O bond first undergoes a homolytic fission under the UV irradiation to give an iminyl radical and a benzoyloxy radical. The iminyl radical then abstracted two hydrogen atoms from 1,4-cyclohexadiene to form imine 8 which was further hydrolyzed to compound 2. The benzoyloxy radical could also capture a hydrogen atom to give benzoic acid (9).

中文摘要.........................................................................i
緒論.................................................................................1
論文研究目標...............................................................12
實驗結果與討論...........................................................14
結論...............................................................................28
使用之儀器、藥品和溶劑...........................................29
實驗步驟與光譜數據...................................................31
參考文獻.......................................................................44
附錄...............................................................................47

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