1-(fluorenyl)-3-phenylgermatrane | 594845-06-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 1-(fluorenyl)-3-phenylgermatrane
• CAS: 594845-06-4
• 化学式: C₂₅H₂₅GeNO₃
• 分子量: 460.068
• InChiKey: DNNUEOJEIQHYOX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  9H-芴-9-基锂 、 1-bromo-3-phenylgermatrane 以 四氢呋喃 、 正己烷 为溶剂， 以61%的产率得到1-(fluorenyl)-3-phenylgermatrane
  参考文献：
  名称：

  Synthesis and characterization of 3- and 4-phenylgermatranes: X-ray crystal structures of N(CH2CH2O)2(CH2CHPhO)GeZ (Z=F, OSiMe3, CCPh) and N(CH2CH2O)2(CHPhCH2O)GeOH

  摘要：

  Reaction of excess of product A [(HOCH2CH2)(2)NCH2CH(Ph)OH (1):(HOCH2CH2)(2)NCH(Ph)CH2OH (2) = 9:1] with GeCl4 led to a mixture of 1-chloro-3-phenylgermatrane (3) and 1-chloro-4-phenylgermatrane (4). Compound 4 was isolated in yield 9% from this mixture. Reaction of (EtO)(3)GeCl with product A gave 3 in yield 55%. 1-(Phenylethynyl)-3-phenylgermatrane (5) was prepared in yield 31% by treatment of (EtO)(3)GeCdropCPh with product A. Reaction of product A with mixture of GeO2 and H2O produced N(CH2CH2O)(2)(CH2CHPhO)GeOH (6) in yield 73%. The presence of N(CH2CH2O)(2)(CHPhCH2O)GeOH (7) among the products of this reaction was confirmed by H-1-, C-13-NMR spectroscopy and X-ray analysis. N(CH2CH2O)(2)(CH2CHPhO)GeF (8) is formed by the treatment of 6 with BF3 . Et2O. N(CH2CH2O)(2)(CH2CHPhO)GeOSiMe3 (9) was obtained by silylation of 6 with (Me3Si)(2)NH or Me3SiCl-Et3N. Refluxing of a suspension of 6 in xylene with continuous removal of water by azeotropic distillation afforded [N(CH2CH2O)(2)(CH(2)CHPh0)Ge](2)O (10). 9 reacted with SOCl2, Me3SiBr and Me3SiOTf to give N(CH2CH2O)(2)(CH2CHPhO)GeX (3, X = Cl; 11, X = Br; 12, X = OTf), respectively. Reaction of 11 with Et3SnOMe led to the formation of N(CH2CH2O)(2)(CH2CHPhO)GeO e (13). Germatranes N(CH2CH2O)(2)(CH2CHPhO)GeY [14, Y = Flu (fluorenyl); 15, Y = N(SiMe3)(2)] were obtained from the nucleophilic substitution of the substituent X in N(CH2CH2O)(2)(CH2CHPhO)GeX (X = OSiMe3, Br) with the corresponding LiY. All compounds were characterized by H-1- and C-13-NMR spectroscopy and mass spectrometry. Single-crystal structures of 5 and 7-9 were determined by X-ray diffraction studies. (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(03)00225-0

文献信息

• Synthesis and characterization of 3- and 4-phenylgermatranes: X-ray crystal structures of N(CH2CH2O)2(CH2CHPhO)GeZ (Z=F, OSiMe3, CCPh) and N(CH2CH2O)2(CHPhCH2O)GeOH
  作者：Ekaterina V. Gauchenova、Sergey S. Karlov、Anastasia A. Selina、Eleonora S. Chernyshova、Andrei V. Churakov、Judith A.K. Howard、Nikolaj A. Troitsky、Stanislav N. Tandura、Jörg Lorberth、Galina S. Zaitseva

  DOI：10.1016/s0022-328x(03)00225-0

  日期：2003.6

  Reaction of excess of product A [(HOCH2CH2)(2)NCH2CH(Ph)OH (1):(HOCH2CH2)(2)NCH(Ph)CH2OH (2) = 9:1] with GeCl4 led to a mixture of 1-chloro-3-phenylgermatrane (3) and 1-chloro-4-phenylgermatrane (4). Compound 4 was isolated in yield 9% from this mixture. Reaction of (EtO)(3)GeCl with product A gave 3 in yield 55%. 1-(Phenylethynyl)-3-phenylgermatrane (5) was prepared in yield 31% by treatment of (EtO)(3)GeCdropCPh with product A. Reaction of product A with mixture of GeO2 and H2O produced N(CH2CH2O)(2)(CH2CHPhO)GeOH (6) in yield 73%. The presence of N(CH2CH2O)(2)(CHPhCH2O)GeOH (7) among the products of this reaction was confirmed by H-1-, C-13-NMR spectroscopy and X-ray analysis. N(CH2CH2O)(2)(CH2CHPhO)GeF (8) is formed by the treatment of 6 with BF3 . Et2O. N(CH2CH2O)(2)(CH2CHPhO)GeOSiMe3 (9) was obtained by silylation of 6 with (Me3Si)(2)NH or Me3SiCl-Et3N. Refluxing of a suspension of 6 in xylene with continuous removal of water by azeotropic distillation afforded [N(CH2CH2O)(2)(CH(2)CHPh0)Ge](2)O (10). 9 reacted with SOCl2, Me3SiBr and Me3SiOTf to give N(CH2CH2O)(2)(CH2CHPhO)GeX (3, X = Cl; 11, X = Br; 12, X = OTf), respectively. Reaction of 11 with Et3SnOMe led to the formation of N(CH2CH2O)(2)(CH2CHPhO)GeO e (13). Germatranes N(CH2CH2O)(2)(CH2CHPhO)GeY [14, Y = Flu (fluorenyl); 15, Y = N(SiMe3)(2)] were obtained from the nucleophilic substitution of the substituent X in N(CH2CH2O)(2)(CH2CHPhO)GeX (X = OSiMe3, Br) with the corresponding LiY. All compounds were characterized by H-1- and C-13-NMR spectroscopy and mass spectrometry. Single-crystal structures of 5 and 7-9 were determined by X-ray diffraction studies. (C) 2003 Elsevier Science B.V. All rights reserved.