6,7:8,9-dibenzo-1,5-dicyano-trans-2,4-bis(4-chlorophenyl)bicyclo<3.2.2>nona-6,8-diene | 109423-46-3

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 芳基四氢萘木脂素
• 英文名称: 6,7:8,9-dibenzo-1,5-dicyano-trans-2,4-bis(4-chlorophenyl)bicyclo<3.2.2>nona-6,8-diene
• 英文别名: (15R,17R)-15,17-bis(4-chlorophenyl)tetracyclo[6.6.3.02,7.09,14]heptadeca-2,4,6,9,11,13-hexaene-1,8-dicarbonitrile
• CAS: 109423-46-3；109423-50-9；138983-86-5
• 化学式: C₃₁H₂₀Cl₂N₂
• 分子量: 491.419
• InChiKey: VNRTUONTRZSBCU-GCFFAKTISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  35.0
• 可旋转键数：
  2.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  47.58
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  9,10-二氰基蒽 、 rac-trans-1,2-bis(4-chlorophenyl)cyclopropane 以 乙腈 为溶剂， 反应 60.0h， 生成 6,7:8,9-dibenzo-1,5-dicyano-cis-2,4-bis(4-chlorophenyl)bicyclo<3.2.2>nona-6,8-diene 、 6,7:8,9-dibenzo-1,5-dicyano-trans-2,4-bis(4-chlorophenyl)bicyclo<3.2.2>nona-6,8-diene
  参考文献：
  名称：

  Photochemistry of 9,10-dicyanoanthracene-1,2-diarylcyclopropane systems. Photocycloaddition and photoisomerization

  摘要：

  The photochemical reactions of 9,10-dicyanoanthracene (DCA)-1,2-diarylcyclopropane (CP) systems have been investigated. In degassed acetonitrile solution, (4-pi + 2-sigma) photocycloaddition between DCA and CP occurred to give cis- and trans-2,4-diaryl-1,5-dicyano-6,7:8,9-dibenzobicyclo[3.2.2]nona-6,8-dienes in a 3:1 ratio in good chemical yields although the quantum yields were not high (PHI = 0.002-0.04). This photocycloaddition did not occur in benzene. The DCA-sensitized photoisomerization of trans- and cis-1,2-bis(4-methoxyphenyl)cyclopropanes (1a and 2a) in acetonitrile efficiently occurred to afford a photostationary mixture containing 1a and 2a in a 95:5 ratio. The photoisomerization was remarkably accelerated by bubbling air, by adding metal salt such as Mg(ClO4)2 and LiBF4, and also by aromatic hydrocarbons such as phenanthrene and biphenyl. The quantum yield for the photoisomerization of 2a to 1a exceeded unity, indicating that this photoisomerization involved a chain process. The DCA-sensitized photoisomerization of optically resolved (-)-1a afforded a racemic mixture of (+)-1a and (-)-1a. These photoreactions are initiated by a one-electron transfer from CP to the excited singlet of DCA. The photocycloaddition proceeds via radical ion pairs in solvent cage and the photoisomerization proceeds via solvent-separated radical cations of CP.

  DOI：

  10.1021/jo00032a045