Bis<2,3:4,5:6,7-tris(bicyclo<2.2.2>octeno)cycloheptatrien-1-yl>acetylene

• 分子结构分类: 有机化合物 - 碳氢化合物 - 多环烃
• 英文名称: Bis<2,3:4,5:6,7-tris(bicyclo<2.2.2>octeno)cycloheptatrien-1-yl>acetylene
• 英文别名: 15-[2-(15-Heptacyclo[15.2.2.24,7.210,13.02,16.03,8.09,14]pentacosa-2(16),3(8),9(14)-trienyl)ethynyl]heptacyclo[15.2.2.24,7.210,13.02,16.03,8.09,14]pentacosa-2(16),3(8),9(14)-triene
• 化学式: C₅₂H₆₂
• 分子量: 687.064
• InChiKey: DEAQOCFFISUHLU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.6
• 重原子数：
  52
• 可旋转键数：
  0
• 环数：
  20.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  Bis<2,3:4,5:6,7-tris(bicyclo<2.2.2>octeno)cycloheptatrien-1-yl>acetylene 在 triphenylmethylium hexafluoroantimonate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 生成 Bisocteno)tropylium>acetylene hexafluoroantimonate
  参考文献：
  名称：

  A Novel Carbodication Composed of Two Tris(bicyclo[2.2.2]octeno)tropylium Units Connected by a Triple Bond: Synthesis, Structure, and Properties

  摘要：

  The titled dication, bis[tris(bicyclo[2.2.2]octeno)tropyliumyl] acetylene dication 3, which is the first example of the acetylene having two tropylium ion units at both ends, has been synthesized by stepwise introduction of the tris(bicyclo[2.2.2]octeno)cycloheptatrienyl unit to acetylene followed by hydride abstraction. The results of X-ray crystallography indicated that the two tropylium rings are twisted with each, other by the angle of 44 degrees and the tropylium ring is slightly bent into a boat form. The dication 3 was neutralized in 50% aqueous acetonitrile via two steps at the pH values of 7.0 and 11.5, which correspond to the pK(R+) values of the dictation and the half-neutralized monocation, respectively. Thus, the dication 3 is 6 pK(R+) units destabilized compared with the corresponding monocation (pK(R+) 13.0) due to the intramolecular electrostatic repulsion of the positive charge. The cyclic voltammetry indicated that the dication 3 undergoes two reversible one-electron reductions consecutively in dichloromethane. The electrochemical reduction of 3 as well as chemical reduction with zinc powder in dichloromethane-acetonitrile afforded a blue solution of the corresponding cation radical 3(.+), but not the diradical, as shown by ESR experiments.

  DOI：

  10.1021/jo00096a051
• 作为产物：
  描述：

  7-Ethynyl-1,2:3,4:5,6-tris(bicyclo<2.2.2>octeno)cycloheptatriene 以48%的产率得到
  参考文献：
  名称：

  Kagayama Akifumi, Komatsu Koichi, Nishinaga Tohru, Takeuchi Kenichi, Kabu+, J. Org. Chem, 59 (1994) N 17, S 4999-5004

  摘要：

  DOI：

文献信息

• Kagayama Akifumi, Komatsu Koichi, Nishinaga Tohru, Takeuchi Kenichi, Kabu+, J. Org. Chem, 59 (1994) N 17, S 4999-5004
  作者：Kagayama Akifumi, Komatsu Koichi, Nishinaga Tohru, Takeuchi Kenichi, Kabu+

  DOI：——

  日期：——
• A Novel Carbodication Composed of Two Tris(bicyclo[2.2.2]octeno)tropylium Units Connected by a Triple Bond: Synthesis, Structure, and Properties
  作者：Akifumi Kagayama、Koichi Komatsu、Tohru Nishinaga、K. Takeuchi、Chizuko Kabuto

  DOI：10.1021/jo00096a051

  日期：1994.8

  The titled dication, bis[tris(bicyclo[2.2.2]octeno)tropyliumyl] acetylene dication 3, which is the first example of the acetylene having two tropylium ion units at both ends, has been synthesized by stepwise introduction of the tris(bicyclo[2.2.2]octeno)cycloheptatrienyl unit to acetylene followed by hydride abstraction. The results of X-ray crystallography indicated that the two tropylium rings are twisted with each, other by the angle of 44 degrees and the tropylium ring is slightly bent into a boat form. The dication 3 was neutralized in 50% aqueous acetonitrile via two steps at the pH values of 7.0 and 11.5, which correspond to the pK(R+) values of the dictation and the half-neutralized monocation, respectively. Thus, the dication 3 is 6 pK(R+) units destabilized compared with the corresponding monocation (pK(R+) 13.0) due to the intramolecular electrostatic repulsion of the positive charge. The cyclic voltammetry indicated that the dication 3 undergoes two reversible one-electron reductions consecutively in dichloromethane. The electrochemical reduction of 3 as well as chemical reduction with zinc powder in dichloromethane-acetonitrile afforded a blue solution of the corresponding cation radical 3(.+), but not the diradical, as shown by ESR experiments.