2-phenylbicyclo<2.2.2>octane | 56139-28-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 2-phenylbicyclo<2.2.2>octane
• 英文别名: 2-Phenylbicyclo[2.2.2]octane
• CAS: 56139-28-7
• 化学式: C₁₄H₁₈
• 分子量: 186.297
• InChiKey: QJODJSOWQNYRDH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2-phenylbicyclo<2.2.2>octane 在 triphenylmethyl perchlorate 、 copper(I) bromide 作用下， 以 乙腈 为溶剂， 生成 spiro[8aH-azulene-3,2'-bicyclo[2.2.2]octane]-1,1,2,2-tetracarbonitrile
  参考文献：
  名称：

  Stereomutation of 7-tropylionorbornane, 2-tropyliobicyclo[2.2.2]octane, and 2-tropylioadamantane: evidence for the intermediacy of heptafulvenes

  摘要：

  The perchlorates of 7-tropylionorbornane (3), 2-tropyliobicyclo[2.2.2]octane (4), and 2-tropylioadamantane (5) were found to undergo stereomutation in acetonitrile at 25-85-degrees-C, as evidenced by following the change in the C-13 NMR spectra of their deuterium-labeled compounds in acetonitrile-d3. Addition of tetracyanoethylene to their solutions in acetonitrile gave the [8 + 2] cycloaddition products of the corresponding heptafulvenes, indicating the intermediacy of the heptafulvenes. This stereomutation was too slow to detect in dichloromethane at the same temperature. Therefore, it is concluded that the stereomutation proceeds through the abstraction of the alpha-hydrogen by acetonitrile as a base followed by the protonation of the heptafulvene intermediate from the rear side. The entropies of activation which are significantly negative and large indicate abstraction of the alpha-hydrogen is the rate-determining step. The enthalpy of activation for the norbornane system (22.1 +/- 1.1 kcal/mol) is about 8 kcal/mol greater than that for the bicyclo[2.2.2]octane system (15.4 +/- 1.1 kcal/mol) and that for the adamantane system (13.1 +/- 1.3 kcal/mol). Molecular mechanics calculations (MMPI, MM2') for the three heptafulvenes and the corresponding phenyl derivatives (instead of the tropylium ions) indicated that the angle strain at the 8-position of the heptafulvenes controls the rate of the steremutation.

  DOI：

  10.1021/jo00003a028
• 作为产物：
  描述：

  2-cyclohexylbicyclo[2.2.2]octane 生成 2-phenylbicyclo<2.2.2>octane
  参考文献：
  名称：

  VOROBEVA, N. S.;ZEMSKOVA, Z. K.;PEXK, T. I.;GOLOVKINA, L. S.;PETROV, AL. +, NEFTEXIMIYA, 28,(1988) N 5, S. 606-612

  摘要：

  DOI：

文献信息

• IKAI, KEIZO;TAKEUCHI, KENICHI;KINOSHITA, TOMOMI;HAGA, KENICHI;KOMATSU, KO+, J. ORG. CHEM., 56,(1991) N, C. 1052-1058
  作者：IKAI, KEIZO、TAKEUCHI, KENICHI、KINOSHITA, TOMOMI、HAGA, KENICHI、KOMATSU, KO+

  DOI：——

  日期：——