9-methoxy-9-benzhydrylfluorene

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 9-methoxy-9-benzhydrylfluorene
• 英文别名: 9-Benzhydryl-9-methoxyfluorene
• 化学式: C₂₇H₂₂O
• 分子量: 362.471
• InChiKey: DFSYVBXUJDIGHT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  9-芴酮 在 正丁基锂 、 2-甲基苯磺酸 作用下， 以 四氢呋喃 、 正己烷 、 苯 为溶剂， 反应 18.0h， 生成 9-methoxy-9-benzhydrylfluorene
  参考文献：
  名称：

  Studies of 9-Fluorenyl Carbocations. Intramolecular Hydride Migration in a Substituted 9-Fluorenyl Carbocation

  摘要：

  The substituted fluorenyl cation, 9-(diphenylmethyl)fluoren-9-yl cation (4), is formed under stable ion conditions (low temperature/strong acid) from its corresponding alcohol 3. This ion is transformed to a substituted diphenyl methyl cation 8 at ambient temperature via an apparent 1,2-hydrogen shift. Irradiation of 9-(diphenylmethyl)fluoren-9-ol in methanol gives products derived from the corresponding cation along with radical-derived products from C-C and C-O homolysis processes. The laser flash photolysis of this alcohol gave a transient corresponding to cation 4. All of the photoproducts are derived from cation 4 or radical pathways. High level MO calculations point to a high barrier (23.8 kcal mol(-1)) for the 1,2-hydride shift. This barrier is the consequence of the minimum energy conformation of this fluorenyl cation which is less than ideal for the periplanar geometry necessary for this process.

  DOI：

  10.1021/jo0009200

文献信息

• Role of single electron transfer in SN2-type substitution reactions of anions with alkyl halides
  作者：F. G. Bordwell、John A. Harrelson

  DOI：10.1021/jo00281a035

  日期：1989.9
• Steric and electrochemical effects on rates of electron transfer and SN2 reactions of 9-(dialkylamino)fluorenide ions with alkyl halides
  作者：F. G. Bordwell、John A. Harrelson

  DOI：10.1021/ja00185a040

  日期：1989.2
• Studies of 9-Fluorenyl Carbocations. Intramolecular Hydride Migration in a Substituted 9-Fluorenyl Carbocation
  作者：Gabriela Mladenova、Lie Chen、Chris F. Rodriquez、K. W. Michael Siu、Linda J. Johnston、Alan C. Hopkinson、Edward Lee-Ruff

  DOI：10.1021/jo0009200

  日期：2001.2.1

  The substituted fluorenyl cation, 9-(diphenylmethyl)fluoren-9-yl cation (4), is formed under stable ion conditions (low temperature/strong acid) from its corresponding alcohol 3. This ion is transformed to a substituted diphenyl methyl cation 8 at ambient temperature via an apparent 1,2-hydrogen shift. Irradiation of 9-(diphenylmethyl)fluoren-9-ol in methanol gives products derived from the corresponding cation along with radical-derived products from C-C and C-O homolysis processes. The laser flash photolysis of this alcohol gave a transient corresponding to cation 4. All of the photoproducts are derived from cation 4 or radical pathways. High level MO calculations point to a high barrier (23.8 kcal mol(-1)) for the 1,2-hydride shift. This barrier is the consequence of the minimum energy conformation of this fluorenyl cation which is less than ideal for the periplanar geometry necessary for this process.