Tricyclo[3.3.1.13,7]decan-2-ol, 2-(tricyclo[3.3.1.13,7]decylidenemethyl)- | 144436-04-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Tricyclo[3.3.1.13,7]decan-2-ol, 2-(tricyclo[3.3.1.13,7]decylidenemethyl)-
• 英文别名: 2-(Adamantylidenemethyl)-2-adamantanol
• CAS: 144436-04-4
• 化学式: C₂₁H₃₀O
• 分子量: 298.469
• InChiKey: VTBGCDSGRJPSSO-JAIQZWGSSA-N

物化性质

• 沸点：
  416.6±13.0 °C(Predicted)
• 密度：
  1.205±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.56
• 重原子数：
  22.0
• 可旋转键数：
  1.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  Tricyclo[3.3.1.13,7]decan-2-ol, 2-(tricyclo[3.3.1.13,7]decylidenemethyl)- 在 氯氟磺酰 、 氟磺酸 作用下， 生成 2-(Adamantylidenemethyl)-2-adamantyl cation
  参考文献：
  名称：

  Preparation and carbon 13 NMR spectroscopic study of the 2-(adamantylidenemethyl)-2-adamantyl and 2-adamantylidene-1,1-dicyclopropylethyl cations

  摘要：

  2-(Adamantylidenemethyl)-2-adamantyl cation (5) was prepared by ionization of 2-(adamantylidenemethyl)-2-adamantanol (9) in FSO3H/SO2ClF or neat FSO3H at -78-degrees-C. In spite of its high inherent steric strain, carbocation 5 is stable up to 80-degrees-C. Its rotational barrier was estimated to be 16.8 kcal/mol on the basis of the coalescence temperature of the C-13 NMR signals of its diastereomeric beta-methylene carbons, which is in agreement with a DELTAH(double dagger) value of 16.5 kcal/mol calculated by MNDO. Similarly, 2-adamantylidene-l,l-dicyclopropylethyl cation (6) was prepared by the ionization of 1,1-dicyclopropyl-2-(2-hydroxy-2-adamantyl)ethanol (12) in SbF5-FSO/SO2ClF or FSO3H/SO2ClF. Carbocation 6 shows a rotational barrier of less than 5 kcal/mol. The small rotational barrier in 6 is interpreted as due to the positive charge stabilizing influence of the adjacent cyclopropyl groups resulting in an unsymmetrically charge-delocalized allylic cation.

  DOI：

  10.1021/jo00050a014
• 作为产物：
  描述：

  2-(Bromomethyl)-2-bromoadamantane 在 potassium tert-butylate 、 叔丁基锂 作用下， 以 乙醚 为溶剂， 反应 1.5h， 生成 Tricyclo[3.3.1.13,7]decan-2-ol, 2-(tricyclo[3.3.1.13,7]decylidenemethyl)-
  参考文献：
  名称：

  Preparation and carbon 13 NMR spectroscopic study of the 2-(adamantylidenemethyl)-2-adamantyl and 2-adamantylidene-1,1-dicyclopropylethyl cations

  摘要：

  2-(Adamantylidenemethyl)-2-adamantyl cation (5) was prepared by ionization of 2-(adamantylidenemethyl)-2-adamantanol (9) in FSO3H/SO2ClF or neat FSO3H at -78-degrees-C. In spite of its high inherent steric strain, carbocation 5 is stable up to 80-degrees-C. Its rotational barrier was estimated to be 16.8 kcal/mol on the basis of the coalescence temperature of the C-13 NMR signals of its diastereomeric beta-methylene carbons, which is in agreement with a DELTAH(double dagger) value of 16.5 kcal/mol calculated by MNDO. Similarly, 2-adamantylidene-l,l-dicyclopropylethyl cation (6) was prepared by the ionization of 1,1-dicyclopropyl-2-(2-hydroxy-2-adamantyl)ethanol (12) in SbF5-FSO/SO2ClF or FSO3H/SO2ClF. Carbocation 6 shows a rotational barrier of less than 5 kcal/mol. The small rotational barrier in 6 is interpreted as due to the positive charge stabilizing influence of the adjacent cyclopropyl groups resulting in an unsymmetrically charge-delocalized allylic cation.

  DOI：

  10.1021/jo00050a014