6-methyl-6-(p-fluorophenyl)fulvene | 78405-51-3

• 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-methyl-6-(p-fluorophenyl)fulvene
• 英文别名: 1-(1-Cyclopenta-2,4-dien-1-ylideneethyl)-4-fluorobenzene
• CAS: 78405-51-3
• 化学式: C₁₃H₁₁F
• 分子量: 186.229
• InChiKey: WQEWPAVSVKTFOK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  0
• 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-fluorophenyl)fulvene 以 氘代苯 为溶剂， 生成 (1S,2R,6S,7R)-10-[1-(4-Fluoro-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-Fluoro-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：

  4-氟苯乙酮 、 sodium cyclopentadienide 以 四氢呋喃 为溶剂， 以82%的产率得到6-methyl-6-(p-fluorophenyl)fulvene
  参考文献：
  名称：

  通往6,6-二取代富烯的改良途径

  摘要：

  通过使环戊二烯酸钠结晶与合适的酮直接反应，可以高收率快速形成在环外位置具有烷基和/或芳基取代基的五叶黄酮。

  DOI：

  10.1016/j.tetlet.2004.07.058

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
• US4264336A
  申请人：——

  公开号：US4264336A

  公开（公告）日：1981-04-28