1-trichloromethylsila-2,10,11-trioxa-6-aza-3,4;8,9;12,13-tris(4',6'-dimethylbenzo) [4.4.4.0^1,6]tricyclotetradecane

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1-trichloromethylsila-2,10,11-trioxa-6-aza-3,4;8,9;12,13-tris(4',6'-dimethylbenzo) [4.4.4.0^1,6]tricyclotetradecane
• 英文别名: 4,6,14,16,21,23-Hexamethyl-1-(trichloromethyl)-2,18,19-trioxa-10-aza-1-silapentacyclo[8.8.8.03,8.012,17.020,25]hexacosa-3,5,7,12,14,16,20,22,24-nonaene；4,6,14,16,21,23-hexamethyl-1-(trichloromethyl)-2,18,19-trioxa-10-aza-1-silapentacyclo[8.8.8.03,8.012,17.020,25]hexacosa-3,5,7,12,14,16,20,22,24-nonaene
• 化学式: C₂₈H₃₀Cl₃NO₃Si
• 分子量: 562.996
• InChiKey: KHOQJNPJHCWFRU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.75
• 重原子数：
  36
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  30.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2,4-二甲基苯酚 在 对甲苯磺酸 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 60.0h， 生成 1-trichloromethylsila-2,10,11-trioxa-6-aza-3,4;8,9;12,13-tris(4',6'-dimethylbenzo) [4.4.4.0^1,6]tricyclotetradecane
  参考文献：
  名称：

  A New Class of Silatranes:  Structure and Dynamic NMR Behavior¹

  摘要：

  A new class of silatranes N[CH2(Me2C6H2)O](3)SiR was prepared by the reaction of organosilanes with tris(2-hydroxy-4,6-dimethylbenzyl) amine (5) in the case of 1, 3, and 4, and by the reaction of Si(OMe)4 with the same amine (5) to give 2. This is the first series of silatranes containing all six-membered rings. Their structures were established by X-ray analysis and correlated with Si-29 NMR data. VT H-1 NMR spectra reflected fluxional behavior for the chiral molecules 1-3, whereas 4 was a rigid molecule. The activation energies for enantiomeric conversion of the clockwise and anticlockwise orientations of the propeller-like silatranes 1-3 were statistically the same at: about 10 kcal/mol. A simultaneous pseudorotation of all three six-membered rings is suggested to cause the racemization process. The Si-N distances for 1-4 show a large dependence on the exocyclic substituent. Over an approximate electronegativity range of 2.3-3.0, the Si-N distance varies from 2.745(4) Angstrom for 1 to 2.025(4) Angstrom for 4. Thus, the influence of substituent effects on nitrogen-silicon donor-acceptor interactions can be readily studied in the absence of constraints imposed by the use of the smaller ring-containing silatranes.

  DOI：

  10.1021/ja9926360

文献信息

• A New Class of Silatranes:  Structure and Dynamic NMR Behavior¹
  作者：A. Chandrasekaran、Roberta O. Day、Robert R. Holmes

  DOI：10.1021/ja9926360

  日期：2000.2.1

  A new class of silatranes N[CH2(Me2C6H2)O](3)SiR was prepared by the reaction of organosilanes with tris(2-hydroxy-4,6-dimethylbenzyl) amine (5) in the case of 1, 3, and 4, and by the reaction of Si(OMe)4 with the same amine (5) to give 2. This is the first series of silatranes containing all six-membered rings. Their structures were established by X-ray analysis and correlated with Si-29 NMR data. VT H-1 NMR spectra reflected fluxional behavior for the chiral molecules 1-3, whereas 4 was a rigid molecule. The activation energies for enantiomeric conversion of the clockwise and anticlockwise orientations of the propeller-like silatranes 1-3 were statistically the same at: about 10 kcal/mol. A simultaneous pseudorotation of all three six-membered rings is suggested to cause the racemization process. The Si-N distances for 1-4 show a large dependence on the exocyclic substituent. Over an approximate electronegativity range of 2.3-3.0, the Si-N distance varies from 2.745(4) Angstrom for 1 to 2.025(4) Angstrom for 4. Thus, the influence of substituent effects on nitrogen-silicon donor-acceptor interactions can be readily studied in the absence of constraints imposed by the use of the smaller ring-containing silatranes.