6-methyl-6-(p-cyanophenyl)fulvene | 91158-23-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 6-methyl-6-(p-cyanophenyl)fulvene
• 英文别名: 4-(1-Cyclopenta-2,4-dien-1-ylideneethyl)benzonitrile
• CAS: 91158-23-5
• 化学式: C₁₄H₁₁N
• 分子量: 193.248
• InChiKey: HQKZNIYEZXUIMF-UHFFFAOYSA-N

物化性质

• 沸点：
  373.4±21.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-苯基马来酰亚胺 、 6-methyl-6-(p-cyanophenyl)fulvene 以 氘代苯 为溶剂， 生成 4-{1-[(1S,2R,6S,7R)-3,5-Dioxo-4-phenyl-4-aza-tricyclo[5.2.1.0^2,6]dec-8-en-(10E)-ylidene]-ethyl}-benzonitrile 、 4-{1-[(1R,2R,6S,7S)-3,5-Dioxo-4-phenyl-4-aza-tricyclo[5.2.1.0^2,6]dec-8-en-(10Z)-ylidene]-ethyl}-benzonitrile
  参考文献：
  名称：

  Can Remote Substituent Effects Influence Reactivity and Stereoselectivity in the Diels-Alder Cycloadditions of p-Substituted 6-Phenyl-6-methylfulvenes?

  摘要：

  The kinetics, activation parameters, and stereoselectivity in the Diels-Alder reaction of a series of p-substituted 6-phenyl-6-methylfulvenes with N-phenylmaleimide have been measured in benzene-d(6) to examine the consequence of remote electronic perturbation on the system. The variation in equilibrium endo:exo ratios as a function of substituent adheres very well to a LFER with sigma(+) (rho = 0.701) in contrast to the kinetic stereoselectivity which shows no linear relationship of the Hammett type. A reasonably good LFER with sigma(-) is observed for the reactivities, especially when the NMe(2) and OMe examples are excluded (rho = -0.684). Temperature and solvent effects on these properties have also been investigated. Substituent-induced changes in preferred conformation and pi-electron densities of the fulvenes have been studied by ab initio molecular orbital calculations. The optimum twist angle between the pi-subsystems remained relatively constant (54-55 degrees) across the series except in the case of p-NMe(2) substitution where it is substantially decreased (36 degrees). Relative reactivities and kinetic stereoselectivities are seen to have a connection with the calculated magnitude and direction of the fulvene molecular dipole moment. The importance of frontier MO energies was examined.

  DOI：

  10.1021/jo00104a031
• 作为产物：
  描述：

  对氰基苯乙酮 、 环戊二烯 反应 1.5h， 以36%的产率得到6-methyl-6-(p-cyanophenyl)fulvene
  参考文献：
  名称：

  Nonalternant systems. 2. Electronic effects of substituents in 6-methyl-6-phenylfulvenes: carbon-13 NMR and theoretical studies

  摘要：

  DOI：

  10.1021/ja00329a056

文献信息

• Nonalternant systems. 2. Electronic effects of substituents in 6-methyl-6-phenylfulvenes: carbon-13 NMR and theoretical studies
  作者：D. J. Sardella、C. M. Keane、P. Lemonias

  DOI：10.1021/ja00329a056

  日期：1984.8
• Can Remote Substituent Effects Influence Reactivity and Stereoselectivity in the Diels-Alder Cycloadditions of p-Substituted 6-Phenyl-6-methylfulvenes?
  作者：M. M. Gugelchuk、P. C.-M. Chan、T. J. Sprules

  DOI：10.1021/jo00104a031

  日期：1994.12

  The kinetics, activation parameters, and stereoselectivity in the Diels-Alder reaction of a series of p-substituted 6-phenyl-6-methylfulvenes with N-phenylmaleimide have been measured in benzene-d(6) to examine the consequence of remote electronic perturbation on the system. The variation in equilibrium endo:exo ratios as a function of substituent adheres very well to a LFER with sigma(+) (rho = 0.701) in contrast to the kinetic stereoselectivity which shows no linear relationship of the Hammett type. A reasonably good LFER with sigma(-) is observed for the reactivities, especially when the NMe(2) and OMe examples are excluded (rho = -0.684). Temperature and solvent effects on these properties have also been investigated. Substituent-induced changes in preferred conformation and pi-electron densities of the fulvenes have been studied by ab initio molecular orbital calculations. The optimum twist angle between the pi-subsystems remained relatively constant (54-55 degrees) across the series except in the case of p-NMe(2) substitution where it is substantially decreased (36 degrees). Relative reactivities and kinetic stereoselectivities are seen to have a connection with the calculated magnitude and direction of the fulvene molecular dipole moment. The importance of frontier MO energies was examined.