4-Homoadamantyl tosylate | 25763-46-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-Homoadamantyl tosylate
• 英文别名: 4-Homoadamantyltosylat；4-tricyclo[4.3.1.13,8]undecanyl 4-methylbenzenesulfonate
• CAS: 25763-46-6
• 化学式: C₁₈H₂₄O₃S
• 分子量: 320.453
• InChiKey: DEJCMKUJECSIGN-UHFFFAOYSA-N

物化性质

• 沸点：
  456.8±14.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.92
• 重原子数：
  22.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-Homoadamantyl tosylate 在 potassium tert-butylate 、 间氯过氧苯甲酸 、 叔丁醇 作用下， 以 二氯甲烷 为溶剂， 生成 Homoadamantanoxid
  参考文献：
  名称：

  Acetolysis of 4-homoadamantyl tosylate. Multiple degenerate rearrangements and mechanism

  摘要：

  DOI：

  10.1021/ja00437a039
• 作为产物：
  描述：

  三环[4.3.1.13,8]十一烷-4-酮 在 吡啶 、 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 4-Homoadamantyl tosylate
  参考文献：
  名称：

  [3-13C] -4-高金刚烷基甲苯磺酸盐的溶剂分解。在溶剂分解条件下，通过多个Wagner-Meerwein重排和邻位氢化物移位，限制了4-高金刚烷基阳离子的简并性。

  摘要：

  The solvolysis of 4-homoadamantyl tosylate in methanol, acetic acid, and 2,2,2-trifluoroethanol yielded 4-substituted homoadamantane and 4-homoadamantene as major products, together with exo-2-substituted homoadamantane and 2,4-dehydrohomoadamantane. The analysis of carbon-13 label distribution in the products from the [3-C-13]-labeled reactant, which provided results complementary to those of Nordlander's deuterium label experiments, showed that the 4-homoadamantyl cation is a classical ion that is rapidly rearranging via the degenerate Wagner-Meerwein process (k(w)). This equilibrium was more nearly complete in less nucleophilic solvents. Another possible degenerate rearrangement, 5,4-hydride shift (k(h)), was shown to be much slower (k(w)/k(h) = 140-760): most of the 4-substituted product is formed with no more than a single hydride shift. Thus, the potential 11-fold degeneracy of the 4-homoadamantyl cation through the two types of rearrangements is partially restricted by competing solvent attack (k(p)). The analysis of the label distribution for the recovered reactant revealed involvement of appreciable ion pair return (k(-i)). The relative rates of the four possible processes concerning the fate of 4-homoadamantyl cation were determined in acetic acid at 40-degrees-C to be k(p):k(-i):k(w):k(h) = 1:3.0:9.7:0.068.

  DOI：

  10.1021/jo00079a039