| 研究生: |
林敏智 Lin, Min-Chih |
|---|---|
| 論文名稱: |
5-氟尿嘧啶衍生物中間體的合成及構形變化的研究 Synthesis and Isomerization studies of Intermediates to 5-Fluorouracil |
| 指導教授: |
宋光生
Sung, Kuangsen |
| 學位類別: |
碩士 Master |
| 系所名稱: |
理學院 - 化學系 Department of Chemistry |
| 論文出版年: | 2004 |
| 畢業學年度: | 92 |
| 語文別: | 中文 |
| 論文頁數: | 75 |
| 中文關鍵詞: | 中間體 、異構化 、5-氟尿嘧啶 |
| 外文關鍵詞: | isomerization, intermediates, 5-Fluorouracil |
| 相關次數: | 點閱:61 下載:1 |
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在有機分子結構上,我們經常見到碳-碳雙鍵的形成是很多合成步驟當中的一種。過去30年來,許多的目前的藥物都已經開始著手研發中間體,因為可利用中間體來製備最後的藥物有著較高的效率,所得的產率也較好,也可有效的降低成本。
我們最初有意利用類似的中間體來合成racil的衍生物,合成的中間體僅得單一一種穩定結構,我們利用gated decoupling 的NMR程式來鑑定分子的conformation,並計算其coupling constant的大小,我們確定中間體分子多以trans 的型態存在較穩定。
最後我們將製備的中間體,測試uv吸收波長和選定不會對背景產生干擾的溶劑,進行光化學實驗,結果發現vinyl ether中間體在254nm有最大吸收,經過照光的反應後,可由最穩定的trans轉變為較不穩定的cis form,但因自然界趨向於最穩定的狀態,因此在室溫下cis form會緩慢的回去最穩定的狀態,而enamine的中間體也許因為轉動的速度太快,以致於無法順利觀測到。
此類的中間體分子吸收合適波長的uv光後,雙鍵上的π電子便被激發至perpendicular triplet state,因此分子中取代基原來由共平面的狀態扭曲至平面外,視不同分子有不同的扭曲角度,這類分子的perpendicular triplet state 為次穩定態,視其機率可回到cis form 與trans form的ground state,因此我們便可以看到利用NMR偵測到的結果,這類分子亦可以週而復始的進行結構上的改變,只要給予合適的能量,這類的分子就可被我們加以掌握,如同分子的開關一般。
Carbon-carbon bond is one of the most important synthetic steps in construction of organic molecules. From now on,many people discuss the intermediate of the Medicine,because it can get more efficiency,more yield,and decrease the cost.
We want to use the derivative of the intermediate to synthesize 5-fluoro uracil, and get one result of trans or cis form alternatively.By gated decoupling and calculate the coupling constants.We make sure that we get trans compound.
The intermediate of vinyl ether ,which have a maximum absorption at 254nm.Stable trans form can inverse to unstable cis form under uv irradiation.Cis form can not be isolated,because it will return to trans form.We the intermediate under uv Irradiation,the πelctrons are excited to perpendicular triplet state,and then substituted group of the molecular will twist out of plane.Molecular will release the energy and return to the ground state of cis and trans form.
The process will regain under uv irradiation,when we provide suitable energy.We can control and regard it as a molecular switch.
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