trimethylsilyl 2-[2-(2-ethoxyethoxy)ethoxy]-2,3,3,3-tetrafluoropropionate | 197356-81-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: trimethylsilyl 2-[2-(2-ethoxyethoxy)ethoxy]-2,3,3,3-tetrafluoropropionate
• 英文别名: Trimethylsilyl 2-[2-(2-ethoxyethoxy)ethoxy]-2,3,3,3-tetrafluoropropanoate
• CAS: 197356-81-3
• 化学式: C₁₂H₂₂F₄O₅Si
• 分子量: 350.383
• InChiKey: DEVRHTFENGEFCA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.66
• 重原子数：
  22
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  trimethylsilyl 2-[2-(2-ethoxyethoxy)ethoxy]-2,3,3,3-tetrafluoropropionate 反应 1.0h， 以63%的产率得到1-[2-(2-乙氧基乙氧基)乙氧基]-1,2,2-三氟乙烯
  参考文献：
  名称：

  Synthesis of Trifluorovinyl Ethers Incorporating Functionalized Hydrocarbon Ether Groups:  Insight into the Mechanism of Trifluorovinyl Ether Formation from Trimethylsilyl 2-Alkoxy-2,3,3,3-tetrafluoropropionates

  摘要：

  Novel trifluorovinyl ethers (TFVEs, ROCF=CF2), where R is an oligoether, were synthesized from the corresponding sodium alkoxide and hexafluoropropene oxide. The sodium alkoxide ring opened hexafluoropropene oxide at the more highly substituted carbon (C2) to give the 2-alkoxy-2,3,3,3-tetrafluoropropionic acid ester incorporating 2 equiv of the alcohol, ROCF(CFB)CO2R. Hydrolysis of the ester and reaction of the resulting sodium 2-alkoxy-2,3,3,3-tetrafluoropropionate with chlorotrimethylsilane gave the trimethylsilyl 2-alkoxy-2,3,3,3-tetrafluoropropionate, ROCF(CF3)CO2-Si(CH3)(3). Gas phase vacuum thermolysis of the trimethylsilyl ester at 140-150 degrees C gave the corresponding TFVEs in 55-63% yields. Thus, 1-[2-(ethoxyethoxy)ethoxy]-1,2,2-trifluoroethene and 1-[2-(2-tert-butoxyethoxy)ethoxy]-1,2,2-trifluoroethene were synthesized from 2-(2-ethoxyethoxy)ethanol and 2-(2-tert-butoxyethoxy)ethanol, respectively. Interestingly, thermolysis of sodium or potassium 2-alkoxy-2,3,3,3-tetrafluoropropionates resulted in negligible to low yields of TFVEs.(1) For example, thermolysis of sodium 2-[2-(ethoxyethoxy)ethoxy]-2,3,3,3-tetrafluoropropionate gave a trifluoroacetate ester, 2-(2-ethoxyethoxy)ethyl trifluoroacetate. Variable temperature F-19 NMR spectroscopy of trimethylsilyl 2-[2-(ethoxyethoxy)ethoxy]-2,3,3,3-tetrafluoropropionate suggests that an equilibrium exists between two structural conformations of these trimethylsilyl esters: one in which there is an intramolecular ''interaction'' of silicon with fluorine and one in which there is no silicon-fluorine interaction. This interaction may affect the outcome of the trimethylsilyl ester thermolysis.

  DOI：

  10.1021/jo971319d
• 作为产物：
  描述：

  三甲基氯硅烷 、 2-(2-Ethoxyethoxy)ethyl 2-[2-(2-ethoxyethoxy)ethoxy]-2,3,3,3-tetrafluoropropanoate 在 sodium hydroxide 、 sodium hydride 作用下， 生成 二乙二醇乙醚 、 Carbitol-trimethylsilylaether 、 trimethylsilyl 2-[2-(2-ethoxyethoxy)ethoxy]-2,3,3,3-tetrafluoropropionate
  参考文献：
  名称：

  Synthesis of Trifluorovinyl Ethers Incorporating Functionalized Hydrocarbon Ether Groups:  Insight into the Mechanism of Trifluorovinyl Ether Formation from Trimethylsilyl 2-Alkoxy-2,3,3,3-tetrafluoropropionates

  摘要：

  Novel trifluorovinyl ethers (TFVEs, ROCF=CF2), where R is an oligoether, were synthesized from the corresponding sodium alkoxide and hexafluoropropene oxide. The sodium alkoxide ring opened hexafluoropropene oxide at the more highly substituted carbon (C2) to give the 2-alkoxy-2,3,3,3-tetrafluoropropionic acid ester incorporating 2 equiv of the alcohol, ROCF(CFB)CO2R. Hydrolysis of the ester and reaction of the resulting sodium 2-alkoxy-2,3,3,3-tetrafluoropropionate with chlorotrimethylsilane gave the trimethylsilyl 2-alkoxy-2,3,3,3-tetrafluoropropionate, ROCF(CF3)CO2-Si(CH3)(3). Gas phase vacuum thermolysis of the trimethylsilyl ester at 140-150 degrees C gave the corresponding TFVEs in 55-63% yields. Thus, 1-[2-(ethoxyethoxy)ethoxy]-1,2,2-trifluoroethene and 1-[2-(2-tert-butoxyethoxy)ethoxy]-1,2,2-trifluoroethene were synthesized from 2-(2-ethoxyethoxy)ethanol and 2-(2-tert-butoxyethoxy)ethanol, respectively. Interestingly, thermolysis of sodium or potassium 2-alkoxy-2,3,3,3-tetrafluoropropionates resulted in negligible to low yields of TFVEs.(1) For example, thermolysis of sodium 2-[2-(ethoxyethoxy)ethoxy]-2,3,3,3-tetrafluoropropionate gave a trifluoroacetate ester, 2-(2-ethoxyethoxy)ethyl trifluoroacetate. Variable temperature F-19 NMR spectroscopy of trimethylsilyl 2-[2-(ethoxyethoxy)ethoxy]-2,3,3,3-tetrafluoropropionate suggests that an equilibrium exists between two structural conformations of these trimethylsilyl esters: one in which there is an intramolecular ''interaction'' of silicon with fluorine and one in which there is no silicon-fluorine interaction. This interaction may affect the outcome of the trimethylsilyl ester thermolysis.

  DOI：

  10.1021/jo971319d

文献信息

• Synthesis of Trifluorovinyl Ethers Incorporating Functionalized Hydrocarbon Ether Groups:  Insight into the Mechanism of Trifluorovinyl Ether Formation from Trimethylsilyl 2-Alkoxy-2,3,3,3-tetrafluoropropionates
  作者：Robert D. Lousenberg、Molly S. Shoichet

  DOI：10.1021/jo971319d

  日期：1997.10.1

  Novel trifluorovinyl ethers (TFVEs, ROCF=CF2), where R is an oligoether, were synthesized from the corresponding sodium alkoxide and hexafluoropropene oxide. The sodium alkoxide ring opened hexafluoropropene oxide at the more highly substituted carbon (C2) to give the 2-alkoxy-2,3,3,3-tetrafluoropropionic acid ester incorporating 2 equiv of the alcohol, ROCF(CFB)CO2R. Hydrolysis of the ester and reaction of the resulting sodium 2-alkoxy-2,3,3,3-tetrafluoropropionate with chlorotrimethylsilane gave the trimethylsilyl 2-alkoxy-2,3,3,3-tetrafluoropropionate, ROCF(CF3)CO2-Si(CH3)(3). Gas phase vacuum thermolysis of the trimethylsilyl ester at 140-150 degrees C gave the corresponding TFVEs in 55-63% yields. Thus, 1-[2-(ethoxyethoxy)ethoxy]-1,2,2-trifluoroethene and 1-[2-(2-tert-butoxyethoxy)ethoxy]-1,2,2-trifluoroethene were synthesized from 2-(2-ethoxyethoxy)ethanol and 2-(2-tert-butoxyethoxy)ethanol, respectively. Interestingly, thermolysis of sodium or potassium 2-alkoxy-2,3,3,3-tetrafluoropropionates resulted in negligible to low yields of TFVEs.(1) For example, thermolysis of sodium 2-[2-(ethoxyethoxy)ethoxy]-2,3,3,3-tetrafluoropropionate gave a trifluoroacetate ester, 2-(2-ethoxyethoxy)ethyl trifluoroacetate. Variable temperature F-19 NMR spectroscopy of trimethylsilyl 2-[2-(ethoxyethoxy)ethoxy]-2,3,3,3-tetrafluoropropionate suggests that an equilibrium exists between two structural conformations of these trimethylsilyl esters: one in which there is an intramolecular ''interaction'' of silicon with fluorine and one in which there is no silicon-fluorine interaction. This interaction may affect the outcome of the trimethylsilyl ester thermolysis.