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研究生:周德全
研究生(外文):Te-Chuan,Chou
論文名稱:氣態一氯三氟乙烯在有機合成上的應用
指導教授:蔡厚仁
學位類別:碩士
校院名稱:國防大學中正理工學院
系所名稱:應用化學研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2007
畢業學年度:95
語文別:中文
中文關鍵詞:一氯三氟乙烯合成團
外文關鍵詞:ChlorotrifluoroetheneSynthon
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本研究使用氣態一氯三氟乙烯 (F2C=CFCl) 取代價錢昂貴且無法進口之一溴三氟乙烯 (F2C=CFBr) 作為反應起始物,從事有機合成的應用實驗。首先在低溫條件下將一氯三氟乙烯以正丁基鋰 (n-BuLi) 進行去鹵化反應,得到 [F2C=CF]-Li+ 中間體,將其分別與氯化苯基二甲基矽 (PhMe2SiCl)、氯化三甲基矽 (Me3SiCl) 及氯化三乙基矽 (Et3SiCl) 進行矽化反應,製得苯基二甲基矽基三氟乙烯 (F2C=CFSiMe2Ph)、三甲基矽基三氟乙烯 (F2C=CFSiMe3) 及三乙基矽基三氟乙烯 (F2C=CFSiEt3)。本研究將上述三類化合物在小粒徑氟化鉀 (KF) 條件下,以二甲基甲醯胺 (DMF) 為溶劑,與氯化三丁基錫 (Bu3SnCl) 進行取代反應,可製得產率不同的三丁基錫三氟乙烯 (F2C=CFSnBu3) 產物。接著將此錫化物進行碘化反應後,並利用Flash蒸餾法製得沸點為30 oC之一碘三氟乙烯 (F2C=CFI),此低沸點物可作為三氟乙烯 (F2C=CF-) 的合成團 (Synthon),利用一氯三氟乙烯為起始物經三步驟合成一碘三氟乙烯的總產率為58 % ,而文獻上從一溴三氟乙烯為反應物合成一碘三氟乙烯的總產率為64 % 。
另一方面,本研究亦以一氯三氟乙烯為起始物在乙醇鈉/乙醇溶液中進行反應合成出CFHClCF2OEt (1-ethoxy-1,1,2-trifluoro-2-chloroethane) 化合物後,再與濃硫酸反應,將二氟亞甲基 (CF2) 轉換成羰基而製備出 CFHClCO2Et (Ethyl chlorofluoroacetate) 化合物,最後將其與亞磷酸三乙酯 ((EtO)3P) 進行 Michaelis-Arbuzov 反應,製得含氟磷酸酯類 (EtO)2P(O)CFHCO2Et (Diethyl (fluorocarbethoxymethyl) phosphonate) 化合物,總產率為56 % ,與文獻上使用一溴三氟為起始物的總產率65 % 差異不大。本研究並對各系列化合物利用核磁共振光譜儀、質譜儀及傅立葉紅外線光譜儀數據做分析鑑定。
Bromotrifluoroethene (F2C=CFBr) is expensive, and it is not allowed to be imported into Taiwan. Base on this situation, this research used the gasous chlorotrifluoroethene (F2C=CFCl) instead of bromotrifluoroethene as starting material to carry out the organic synthetic work. Treatment of chlorotrifluoroethene with n-butyllithium (n-BuLi) gave salt of [F2C=CF]-Li+ which underwent the silylation with chlorodimethylphenylsilane (PhMe2SiCl), trimethylsilyl chloride (Me3SiCl) and triethylsilyl chloride (Et3SiCl) to afford dimethylphenylsilyl trifluoroethylene (F2C=CFSiMe2Ph), trimethylsilyltrifluoroethylene (F2C=CFSiMe3) and triethyls ilyltrifluoroethylene. (F2C=CFSiEt3), respectively. In the presene of potassium fluoride and dimethylformamide (DMF) as solvent, reaction of the silylated compounds F2C=CFSiR3 with tributyltinchloride (Bu3SnCl) provided the tributyltintrifluoroethene (F2C=CFSnBu3) compound. Substitation of tributyltin group with iodine was carried out under a flash distillation to achieve the iodotrifluoroethene (F2C=CFI) which the boiling point is 30 oC. The total yields from chlorotrifluoroethene to iodotrifluoroethene was 58 %.
This reseach also used chlorotrifluoroethene as a starting material to prepare the phosphono-containing compound fluorocarbethoxymethylphosphonate ((EtO)2P(O) CFHCO2Et), Treatment of chlorotrifluoroethene with sodium ethoxide gave 1- ethoxy-1,1,2-trifluoro-2-chloroethene (CFHClCF2OEt) with sequently converted the CF2 group into carbonyl group under sulfuric acid to achieve ethyl chloro fluoroacetate CFHClCO2Et. Finally, the fluoro-containing phosphonate (EtO)2 P(O)CFHCO2Et was synthesized via Michaelis-Arbuzov reaction by reaction of triethylphosphite (EtO)3P with CFHClCO2Et. The total yield from chlorotri fluoroethene to (EtO)2P(O)CFHCO2Et was 56 %. The Nuclear Magnetic Resonance (1H、13C、19F、31P NMR), Mass spectrometer and Fourier Transform Infared Spectrometer (FTIR) spectra were used to identify the structure of the compounds.
目錄

誌謝.... ii
摘要…. iii
ABSTRACT iv
目錄……. vi
表目錄 viii
圖目錄 viii
1. 前言 1
2. 實驗部份 7
2.1 實驗藥品 7
2.2 實驗儀器 10
2.3 實驗步驟 11
2.3.1 由一氯三氟乙烯 (F2C=CFCl) 合成苯基二甲基矽基
三氟乙烯(F2C=CFSiMe2Ph)…………….……………...……………...11
2.3.2 由一氯三氟乙烯 (F2C=CFCl) 合成三甲基矽基三氟
乙烯 (F2C=CFSiMe3)………………………………………………….13
2.3.3 由一氯三氟乙烯 (F2C=CFCl) 合成三乙基矽基三氟
乙烯 (F2C=CFSiEt3)………………………….………………………..17
2.3.4 由三乙基矽基三氟乙烯 (F2C=CFSiEt3) 合成
三丁基錫三氟乙烯 (F2C=CFSnBu3)……………………………….…23
2.3.5 由三甲基矽基三氟乙烯 (F2C=CFSiMe3) 合成
三丁基錫三氟乙烯 (F2C=CFSnBu3)……………………………….…29
2.3.6 由苯基二甲基矽基三氟乙烯 (F2C=CFSiMe2Ph) 合成
三丁基錫三氟乙烯 (F2C=CFSnBu3)……………………………….…29
2.3.7 由三丁基錫三氟乙烯 (F2C=CFSnBu3) 合成
一碘三氟乙烯 (F2C=CFI)………………………….………………….30
2.3.8 由一氯三氟乙烯 (F2C=CFCl) 合成CFHClCF2OEt化合物..…………34
2.3.9 由CFHClCF2OEt合成CFHClCO2Et化合物…………………………..36
2.3.10 由CFHClCO2Et合成 (EtO)2P(O)CFHCO2Et化合物...........................38
3. 結果與討論 41
3.1 一碘三氟乙烯 (F2C=CFI) 合成團製備…………………………………...41
3.2 含氟磷酸酯類 (EtO)2P(O)CFHCO2Et 合成團製備………………………51
4. 結論 55
5. 參考文獻 56
6. 自傳………………………………………………………………………………59
參考文獻

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