trimethyl-[2,2,2-trifluoro-1,1-bis-(4-fluoro-phenyl)-ethoxy]-silane

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: trimethyl-[2,2,2-trifluoro-1,1-bis-(4-fluoro-phenyl)-ethoxy]-silane
• 英文别名: 1-trimethylsilyloxy-1,1-bis(4-fluorophenyl)-2,2,2-trifluoroethane；Trimethyl-[2,2,2-trifluoro-1,1-bis(4-fluorophenyl)ethoxy]silane
• 化学式: C₁₇H₁₇F₅OSi
• 分子量: 360.399
• InChiKey: QZCRFBDLRUHZQM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.62
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  (三氟甲基)三甲基硅烷 、 4,4'-二氟二苯甲酮 在 十二/十四烷基二甲基氧化胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以69%的产率得到trimethyl-[2,2,2-trifluoro-1,1-bis-(4-fluoro-phenyl)-ethoxy]-silane
  参考文献：
  名称：

  Facile Synthesis of TMS-Protected Trifluoromethylated Alcohols Using Trifluoromethyltrimethylsilane (TMSCF₃) and Various Nucleophilic Catalysts in DMF

  摘要：

  Organofluorine compounds are becoming increasingly important in different fields, such as material science, agro chemistry, and the pharmaceutical industry. Nucleophilic trifluoromethylation is one of the widely used methods to incorporate a trifluoromethyl moiety into organic molecules. We have carried out extensive studies to develop varieties of easily accessible nucleophilic catalysts to promote such reactions. TMS-protected trifluoromethylated alcohols were prepared from both aldehydes and ketones in excellent yields using catalytic amount of amine N-oxide. Carbonate and phosphate salts also showed efficient catalytic activity toward this reaction. These reactions were highly solvent dependent, and DMF was found to be the most suitable one among the various solvents studied. All these reactions proceeded under very mild conditions, giving clean products and avoiding the use of any fluoride initiators or expensive catalysts, and extremely water-free conditions. The mechanism for the reaction is discussed in detail. DFT calculations were performed on the possible reaction intermediates using the Gaussian 03 program at B3LYP/6-311+G* level to support the proposed mechanism.

  DOI：

  10.1021/jo060835d

文献信息

• Nucleophilic Trifluoromethylation of Carbonyl Compounds and Disulfides with Trifluoromethane and Silicon-Containing Bases
  作者：Sylvie Large、Nicolas Roques、Bernard R. Langlois

  DOI：10.1021/jo000150s

  日期：2000.12.1

  Provided that DMF (or another N,N-dialkylformamide) is present in the reaction medium, at least in a catalytic amount, fluoroform trifluoromethylates efficiently carbonyl compounds, even enolizable ones, when opposed to (TMS)(2)N- M+, generated in situ from N(TMS)(3) and M+ F- or RO- Na+ When F- is used ina catalytic amount, silylated alpha-(trifluoromethyl)carbinols are-obtained: in this case, the four-component system HCF3/N(TMS)(3)/catalytic F-/catalytic DMF behaves like the Ruppert's reagent, especially as far as nonenolizable carbonyl compounds are concerned (CF3SiMe3 remains more efficient for enolizable carbonyl compounds). This process involves an adduct between DMF and -CF3 which is the true trifluoromethylating agent. In the same way, fluoroform efficiently trifluoromethylates disulfides and diselenides when deprotonated with a strong base selected from t-BuOK or N(SiMe3)(3)/Me4NF (or TBAT). t-BuOK is more adapted to the trifluoromethylation of aryl disulfides whereas N(SiMe3)(3)/F- is well suited to that of aliphatic disulfides.
• Facile Synthesis of TMS-Protected Trifluoromethylated Alcohols Using Trifluoromethyltrimethylsilane (TMSCF₃) and Various Nucleophilic Catalysts in DMF
  作者：G. K. Surya Prakash、Chiradeep Panja、Habiba Vaghoo、Vijayalakshmi Surampudi、Roman Kultyshev、Mihirbaran Mandal、Golam Rasul、Thomas Mathew、George A. Olah

  DOI：10.1021/jo060835d

  日期：2006.9.1

  Organofluorine compounds are becoming increasingly important in different fields, such as material science, agro chemistry, and the pharmaceutical industry. Nucleophilic trifluoromethylation is one of the widely used methods to incorporate a trifluoromethyl moiety into organic molecules. We have carried out extensive studies to develop varieties of easily accessible nucleophilic catalysts to promote such reactions. TMS-protected trifluoromethylated alcohols were prepared from both aldehydes and ketones in excellent yields using catalytic amount of amine N-oxide. Carbonate and phosphate salts also showed efficient catalytic activity toward this reaction. These reactions were highly solvent dependent, and DMF was found to be the most suitable one among the various solvents studied. All these reactions proceeded under very mild conditions, giving clean products and avoiding the use of any fluoride initiators or expensive catalysts, and extremely water-free conditions. The mechanism for the reaction is discussed in detail. DFT calculations were performed on the possible reaction intermediates using the Gaussian 03 program at B3LYP/6-311+G* level to support the proposed mechanism.