4-Methoxyhomoadamantane | 29542-64-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-Methoxyhomoadamantane
• 英文别名: 4-Homoadamantyl-methylether；4-Methoxyhomoadamantan；4-methoxytricyclo[4.3.1.13,8]undecane
• CAS: 29542-64-1
• 化学式: C₁₂H₂₀O
• 分子量: 180.29
• InChiKey: OBMBRZTXVPKCTM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.85
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  4-homoadamantanol 在 吡啶 、 2,6-二甲基吡啶 作用下， 以 甲醇 为溶剂， 生成 4-Methoxyhomoadamantane
  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

• Solvolysis of 3-substituted 4-homoadamantyl methanesulphonates. Can the ?-substituent effect distinguish between classical and non-classical ion intermediates?
  作者：Takao Okazaki、Toshikazu Kitagawa、Ken'Ichi Takeuchi

  DOI：10.1002/poc.610070904

  日期：1994.9

  that 3 (R = H) solvolyses via a classical ion intermediate. The logarithms of the solvolysis rate constants of 3 showed linear correlations with those of 1-R-2-adamantyl tosylates (1) and 1-R-exo-2-norbornyl tosylates (2), indicating that the linear free-energy relationship between the β-substituent effects on the solvolysis rate is not a definite measure to distinguish between classical and non-classical

  在80％的乙醇水溶液中测定3-R-4-高金刚烷基甲磺酸盐（甲磺酸盐）（3）的溶剂分解速率。25°C时相对一阶速率常数为1·0（R = H），2·29（R = Ph），3·26（R = p-茴香基），73·6（R = Me）和209（R = Et）。3的甲醇分解反应产生了重排的甲醚和重排的烯烃，以及少量（0·9–3·4％）的未重排产物。加速作用的阶数表明，尽管3（R = H）通过经典离子中间体溶剂化，但过渡态仍涉及大量的σ参与。溶剂分解速率常数3的对数与1-R-2-金刚烷基甲苯磺酸盐（1）和1-R- exo的对数显示线性相关-2-降冰片烷基甲苯磺酸酯（2），表明β取代基对溶剂分解速率的线性自由能关系不是区分经典和非经典中间体的明确方法。
• The Synthesis of 2,4-Dehydrohomoadamantane
  作者：Ryohei Yamaguchi、Takeo Katsushima、Mituyosi Kawanisi

  DOI：10.1246/bcsj.47.2830

  日期：1974.11

  A synthesis of 2,4-dehydrohomoadamantane (I) is described. a) The UV irradiation of a solution of 4-homoadamantene (IV) in xylene containing a small amount of methanesulfonic acid under nitrogen gave a 2: 1 mixture of I and IV after 7 day; this mixture afforded pure I in a 40% isolation yield. b) The oxidation of 4-homoadamantyl hydrazone (XI) by Pb(OAc)4, NiPO, and MnO2 (active) gave a 7–11: 1 mixture

  描述了 2,4-脱氢高金刚烷 (I) 的合成。a) 4-高金刚烷 (IV) 在含有少量甲磺酸的二甲苯中的溶液在氮气下的紫外线照射，7 天后得到 I 和 IV 的 2:1 混合物；该混合物以 40% 的分离产率提供纯 I。b) Pb(OAc)4、NiPO 和 MnO2（活性）氧化 4-高金刚烷基腙（XI）分别得到 7-11:1 的 I 和 IV 混合物。观察到 I 与 IV 的比率取决于反应温度，并且在 -78 °C 下 Pb(OAc)4 对 XI 的氧化产生的 I 是 IV 的 30 倍。在 NiPO 和 MnO2 的情况下，添加 MeOH 作为质子源降低了 I 与 IV 的比率。4-高金刚烷基甲苯磺酰腙 (II) 的 Bamford-Stevens 反应在非质子和质子溶剂中进行。I 与 IV 的比率在非质子和质子条件下颠倒。通过考虑构象来解释XI氧化的选择性和II的Bamford-Stevens反应。
• van Zorge,J.A. et al., Recueil des Travaux Chimiques des Pays-Bas, 1970, vol. 89, p. 781 - 790
  作者：van Zorge,J.A. et al.

  DOI：——

  日期：——
• Solvolysis of [3-13C]-4-homoadamantyl tosylate. Limited degeneracy of 4-homoadamantyl cation via multiple Wagner-Meerwein rearrangement and vicinal hydride shifts under solvolytic conditions
  作者：Toshikazu Kitagawa、Takao Okazaki、Koichi Komatsu、Kenichi Takeuchi

  DOI：10.1021/jo00079a039

  日期：1993.12

  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.