4,12-diphenyl-1,7,9,15-tetraoxa-4,12-diaza-8-germaspiro[7.7]pentadecane | 860453-55-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4,12-diphenyl-1,7,9,15-tetraoxa-4,12-diaza-8-germaspiro[7.7]pentadecane
• 英文别名: 4,12-Diphenyl-1,7,9,15-tetraoxa-4,12-diaza-8-germaspiro[7.7]pentadecane
• CAS: 860453-55-0
• 化学式: C₂₀H₂₆GeN₂O₄
• 分子量: 431.027
• InChiKey: RTELFECORXKBJK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.53
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  N,N-二羟乙基苯胺 、 tetraethoxygermanium 以 苯 为溶剂， 以44%的产率得到4,12-diphenyl-1,7,9,15-tetraoxa-4,12-diaza-8-germaspiro[7.7]pentadecane
  参考文献：
  名称：

  Synthesis, X-ray Diffraction Studies, and DFT Calculations on Hexacoordinated Germanium Derivatives:  The Case of Germaspirobis(ocanes)

  摘要：

  Synthesis of the title compounds, viz. [RN(CH2CHR'O)(2)](2)Ge (1, R = Me, R' = H; 2, R = Me, R' = Ph; 3, R = Ph, R' H), by the reaction of 2 equiv of corresponding dialkanolamines RN(CH2CHR'OH)(2) (4, R = Me, R' = H; 5, R Me, R' = Ph; 6, R = Ph, R' = H) with (AIkO)(4)Ge is reported. Composition and structures of all novel compounds were established by H-1 and C-13 NMR spectroscopy and mass spectrometry as well as elemental analysis data. The single-crystal X-ray diffraction of 2 has clearly indicated the presence of two transannular interactions Ge <- N in the compound. N atoms are cis-orientated. The compound 3 possesses long Ge center dot center dot center dot N distances. The structural data obtained from geometry optimizations by DFT calculations on 1-3 reproduces experimental results. Both cis- and trans-isomers were studied, and cis-configuration was found to be more thermodynamically stable for all three compounds. The transition states for possible cis <-> trans rearrangement processes in 1-3 were calculated. The properties of the Ge-O and Ge-N bonds in 1-3 were analyzed by the AIM approach. The interactions between the Ge atom and N atoms as well as 0 atoms possess predominantly ionic character.

  DOI：

  10.1021/ic048165m

文献信息

• Synthesis, structure, and reactivity of germanium-containing derivatives of substituted diethanolamines
  作者：E. Kh. Lermontova、A. V. Churakov、M. Quan、Yu. F. Oprunenko、S. S. Karlov、G. S. Zaitseva

  DOI：10.1134/s0036023609020077

  日期：2009.2

  The reaction of dialkanolamines RN(CH2CH2O)(CHR'CHR'OH) (R = Me, Ph, PhCH2; R' = H, Ph) with tetraethoxygermane gives either 2,2-diethoxy-1,3,6,2-dioxazagermocanes RN(CH2CH2O)(CHR'CHR'O) Ge(OEt)(2) or 1,7,9,15-tetraoxa-4,12-diaza-8-germaspiro[7.7] pentadecanes [RN(CH2CH2O) (CHR'CHR'O)](2)Ge depending on the reactant ratio. The chemical behavior of the obtained compounds in substitution reactions at germanium was studied. The product structure was confirmed by elemental analysis data and H-1, C-13, and F-19 NMR spectroscopy. The cyclotrigermanoxane [MeN(CH2CH2O)(2)GeO](3) was studied by X-ray diffraction.
• Synthesis, X-ray Diffraction Studies, and DFT Calculations on Hexacoordinated Germanium Derivatives:  The Case of Germaspirobis(ocanes)
  作者：Sergey S. Karlov、Elmira Kh. Lermontova、Maxim V. Zabalov、Anastasia A. Selina、Andrei V. Churakov、Judith A. K. Howard、Mikhail Yu. Antipin、Galina S. Zaitseva

  DOI：10.1021/ic048165m

  日期：2005.6.1

  Synthesis of the title compounds, viz. [RN(CH2CHR'O)(2)](2)Ge (1, R = Me, R' = H; 2, R = Me, R' = Ph; 3, R = Ph, R' H), by the reaction of 2 equiv of corresponding dialkanolamines RN(CH2CHR'OH)(2) (4, R = Me, R' = H; 5, R Me, R' = Ph; 6, R = Ph, R' = H) with (AIkO)(4)Ge is reported. Composition and structures of all novel compounds were established by H-1 and C-13 NMR spectroscopy and mass spectrometry as well as elemental analysis data. The single-crystal X-ray diffraction of 2 has clearly indicated the presence of two transannular interactions Ge <- N in the compound. N atoms are cis-orientated. The compound 3 possesses long Ge center dot center dot center dot N distances. The structural data obtained from geometry optimizations by DFT calculations on 1-3 reproduces experimental results. Both cis- and trans-isomers were studied, and cis-configuration was found to be more thermodynamically stable for all three compounds. The transition states for possible cis <-> trans rearrangement processes in 1-3 were calculated. The properties of the Ge-O and Ge-N bonds in 1-3 were analyzed by the AIM approach. The interactions between the Ge atom and N atoms as well as 0 atoms possess predominantly ionic character.