氣態一氯三氟乙烯在有機合成上的應用

• Main Authors: Te-Chuan,Chou, 周德全
• Other Authors: 蔡厚仁
• Format: Others
• Language: zh-TW
• Published: 2007
• Online Access: http://ndltd.ncl.edu.tw/handle/62354275819988791083

碩士 === 國防大學中正理工學院 === 應用化學研究所 === 95 === 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.