6-(p-(Dimethylamino)phenyl)-6-methylfulvene | 167752-00-3

• 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-(p-(Dimethylamino)phenyl)-6-methylfulvene
• 英文别名: 6-(4-(dimethylamino)phenyl)-6-methylfulvene；Benzenamine, 4-[1-(2,4-cyclopentadien-1-ylidene)ethyl]-N,N-dimethyl-；4-(1-cyclopenta-2,4-dien-1-ylideneethyl)-N,N-dimethylaniline
• CAS: 167752-00-3
• 化学式: C₁₅H₁₇N
• 分子量: 211.307
• InChiKey: QOJSYQWFJYRLRD-UHFFFAOYSA-N

物化性质

• 沸点：
  365.5±21.0 °C(Predicted)
• 密度：
  1.051±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  3.2
• 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-(p-(Dimethylamino)phenyl)-6-methylfulvene 以 氘代苯 为溶剂， 生成 (1S,2R,6S,7R)-10-[1-(4-Dimethylamino-phenyl)-eth-(E)-ylidene]-4-phenyl-4-aza-tricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione 、 (1R,2R,6S,7S)-10-[1-(4-Dimethylamino-phenyl)-eth-(Z)-ylidene]-4-phenyl-4-aza-tricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione
  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：

  环戊二烯 、 二甲氨基苯乙酮 在 氢氧化钾 作用下， 以 甲醇 为溶剂， 以12%的产率得到6-(p-(Dimethylamino)phenyl)-6-methylfulvene
  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

文献信息

• 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.