1-(trifluorosilylmethyl)-2-oxoperhydroazepine | 132363-59-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: 1-(trifluorosilylmethyl)-2-oxoperhydroazepine
• CAS: 132363-59-8
• 化学式: C₇H₁₂F₃NOSi
• 分子量: 211.259
• InChiKey: YFGGWQFJLGIKDS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.78
• 重原子数：
  13.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  20.31
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  18-冠醚-6 、 1-(trifluorosilylmethyl)-2-oxoperhydroazepine 、 甲苯 在 potassium fluoride 作用下， 以 苯 为溶剂， 以70%的产率得到potassium 18-crown-6-(2-oxoperhydroazepinomethyl)tetrafluorosilicate, monosolvate with toluene
  参考文献：
  名称：

  Synthesis, structure and dynamic stereochemistry of (O→Si)-chelate N-(trifluorosilylmethyl)-[N-(S)-(1-phenylethyl)]acetamide and 1-(trifluorosilylmethyl)-2-oxoperhydroazepine: Retention of the O→Si coordination in the adduct with KF and 18-crown-6

  摘要：

  The novel compounds, N-(trifluorosilylmethyl)-[N-(S)-(1-phenylethyl)]- acetamide (1a) and 1-(trifluorosilylmethyl)- 2-oxoperhydroazepine (1b) have been prepared from the corresponding NH-compounds using ClCH2SiCl3/Et3N or ClCH2SiCl3/(Me3Si)(2)NH followed by methanolysis or hydrolysis of the reaction mixture in the presence of Lewis bases, and then BF3 etherate. Potassium-(18-crown-6)-(2-oxoperhydroazepinomethyl) tetrafluorosilicate (2) was synthesized by reaction of the trifluoride (1b) with KF in the presence of 18-crown-6. Using F-19, Si-29 NMR and X-ray diffraction techniques it was established that the silicon atom is pentacoordinate in the trifluorides (1a, b) and hexacoordinate in the adduct 2. Thus the internal coordination of the O --> Si bond present in the trifluoride (1b) is retained in the adduct 2. The stereochemical non-rigidity of the trifluorides (1a, b) and the N-(trifluorosilylmethyl)-N-methylacetamide (1c) was investigated using dynamic F-19 NMR spectroscopy. The activation barriers for permutational isomerization are in the range 9.5-10 kcal mol(-1). Lower values of Delta G(#) for permutation of trifluorides (1a-c) compared to the monofluorides with the coordination core OSiC3F together with small negative values for the activation entropy implies a non-dissociative mechanism. Quantum-chemical analysis suggests a mechanism involving a turnstile rotation. (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.01.033
• 作为产物：
  描述：

  己内酰胺 、 (氯甲基)三氯硅烷 在 三乙胺 、 甲醇 、 三氟化硼乙醚 作用下， 以 苯 为溶剂， 反应 0.5h， 以60%的产率得到1-(trifluorosilylmethyl)-2-oxoperhydroazepine
  参考文献：
  名称：

  Synthesis, structure and dynamic stereochemistry of (O→Si)-chelate N-(trifluorosilylmethyl)-[N-(S)-(1-phenylethyl)]acetamide and 1-(trifluorosilylmethyl)-2-oxoperhydroazepine: Retention of the O→Si coordination in the adduct with KF and 18-crown-6

  摘要：

  The novel compounds, N-(trifluorosilylmethyl)-[N-(S)-(1-phenylethyl)]- acetamide (1a) and 1-(trifluorosilylmethyl)- 2-oxoperhydroazepine (1b) have been prepared from the corresponding NH-compounds using ClCH2SiCl3/Et3N or ClCH2SiCl3/(Me3Si)(2)NH followed by methanolysis or hydrolysis of the reaction mixture in the presence of Lewis bases, and then BF3 etherate. Potassium-(18-crown-6)-(2-oxoperhydroazepinomethyl) tetrafluorosilicate (2) was synthesized by reaction of the trifluoride (1b) with KF in the presence of 18-crown-6. Using F-19, Si-29 NMR and X-ray diffraction techniques it was established that the silicon atom is pentacoordinate in the trifluorides (1a, b) and hexacoordinate in the adduct 2. Thus the internal coordination of the O --> Si bond present in the trifluoride (1b) is retained in the adduct 2. The stereochemical non-rigidity of the trifluorides (1a, b) and the N-(trifluorosilylmethyl)-N-methylacetamide (1c) was investigated using dynamic F-19 NMR spectroscopy. The activation barriers for permutational isomerization are in the range 9.5-10 kcal mol(-1). Lower values of Delta G(#) for permutation of trifluorides (1a-c) compared to the monofluorides with the coordination core OSiC3F together with small negative values for the activation entropy implies a non-dissociative mechanism. Quantum-chemical analysis suggests a mechanism involving a turnstile rotation. (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.01.033