4-Homoadamantyl acetate | 40556-91-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 4-Homoadamantyl acetate
• 英文别名: 4-Homoadamantyl-acetat；4-tricyclo[4.3.1.13,8]undecanyl acetate
• CAS: 40556-91-0
• 化学式: C₁₃H₂₀O₂
• 分子量: 208.301
• InChiKey: TWTBIVKMOHXDIJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.76
• 重原子数：
  15.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  三环[4.3.1.13,8]十一烷-4-酮 在 吡啶 、 lithium aluminium tetrahydride 、 sodium acetate 作用下， 以 乙醚 、 溶剂黄146 为溶剂， 生成 4-Homoadamantyl acetate
  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

文献信息

• Acetolysis of 4-homoadamantyl tosylate. Multiple degenerate rearrangements and mechanism
  作者：J. Eric Nordlander、John B. Hamilton、Felicia Y. H. Wu、Satya P. Jindal、Robert R. Gruetzmacher

  DOI：10.1021/ja00437a039

  日期：1976.10