9‐cyano‐9,9'-bifluorenyl | 17454-96-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 9‐cyano‐9,9'-bifluorenyl
• 英文别名: 9,9'-bifluorene-9-carbonitrile；9-cyano-9,9'-bifluorene；<9,9'>Bifluorenyl-9-carbonitril；9-Cyano-9,9'-bifluoren；9-(9H-fluoren-9-yl)fluorene-9-carbonitrile
• CAS: 17454-96-5
• 化学式: C₂₇H₁₇N
• 分子量: 355.439
• InChiKey: AWIORBHFTRRGMM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  28
• 可旋转键数：
  1
• 环数：
  6.0
• 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：

  9‐cyano‐9,9'-bifluorenyl 在 甲醇 作用下， 反应 0.25h， 以13%的产率得到芴
  参考文献：
  名称：

  光化学生成9-氟烯基

  摘要：

  在较少极性的溶剂中辐照一系列9 H-芴醇和9 H，9'H-联芴基，得到由其相应的9 H-芴基自由基衍生的光产物。通过激光闪光光解法直接观察到这些瞬态物质，并将其紫外/可见光谱与其相应阳离子的光谱进行比较。这些中间体的理论计算（密度泛函理论[DFT]）表明，它们的不稳定性质与相应阳离子的抗芳烃特征相似。

  DOI：

  10.1002/poc.3920
• 作为产物：
  描述：

  芴-9-硫酮 在 高氯酸 、 三苯基膦 作用下， 以 二甲基亚砜 、 乙腈 为溶剂， 反应 5.0h， 生成 9‐cyano‐9,9'-bifluorenyl
  参考文献：
  名称：

  9-Fluorenyl 9-(p-tolylsulfonyl)-9-fluorenyl disulfide: the unexpected product of the reaction of 9-bromofluorene and potassium p-toluenethiosulfonate and the mechanism of its formation

  摘要：

  Reaction of potassium p-toluenethiosulfonate with 9-bromofluorene leads, not to the expected 9-fluorenyl p-toluenethiosulfonate (3), but rather to a product shown to be 9-fluorenyl 9-(p-tolylsulfonyl)-9-fluorenyl disulfide (7, R = 9-fluorenyl) (eq 11). This disulfide of unusual structure is shown to arise as a result of the following reaction sequence: (a) initial formation of 3; (b) a facile elimination of 3 (due to the acidity of the 9-H), forming p-toluenesulfinic acid and 9-thiofluorenone (4); (c) addition of p-CH3C6HSO2- to 4 to give alpha-sulfonyl thiolate ion 16; and (d) reaction of 16 with remaining 3 (in a rapid displacement at the dicoordinate sulfur) to give 7 plus regeneration of p-CH3C6H4SO2-.

  DOI：

  10.1021/jo00021a036

文献信息

• Braven, J.; Hanson, R. W.; Smith, N. G., Journal of Heterocyclic Chemistry, 1995, vol. 32, # 3, p. 1051 - 1056
  作者：Braven, J.、Hanson, R. W.、Smith, N. G.

  DOI：——

  日期：——
• 9-Fluorenyl 9-(p-tolylsulfonyl)-9-fluorenyl disulfide: the unexpected product of the reaction of 9-bromofluorene and potassium p-toluenethiosulfonate and the mechanism of its formation
  作者：John L. Kice、Tatianna G. Kutateladze、Lidia Kupczyk-Subotkowska

  DOI：10.1021/jo00021a036

  日期：1991.10

  Reaction of potassium p-toluenethiosulfonate with 9-bromofluorene leads, not to the expected 9-fluorenyl p-toluenethiosulfonate (3), but rather to a product shown to be 9-fluorenyl 9-(p-tolylsulfonyl)-9-fluorenyl disulfide (7, R = 9-fluorenyl) (eq 11). This disulfide of unusual structure is shown to arise as a result of the following reaction sequence: (a) initial formation of 3; (b) a facile elimination of 3 (due to the acidity of the 9-H), forming p-toluenesulfinic acid and 9-thiofluorenone (4); (c) addition of p-CH3C6HSO2- to 4 to give alpha-sulfonyl thiolate ion 16; and (d) reaction of 16 with remaining 3 (in a rapid displacement at the dicoordinate sulfur) to give 7 plus regeneration of p-CH3C6H4SO2-.
• Photochemical generation of 9‐Fluorenyl radicals
  作者：Ian R. Duffy、William J. Leigh、Hanan Afifi、Abdelaziz Ebead、René Fournier、Edward Lee‐Ruff

  DOI：10.1002/poc.3920

  日期：2019.4

  corresponding 9H‐fluorenyl radicals. These transient species were directly observed by laser flash photolysis and their UV/visible spectra compared with those of their corresponding cations. Theoretical calculations (density functional theory [DFT]) of these intermediates indicate their destabilizing nature in similar fashion to the antiaromatic character of the corresponding cations.

  在较少极性的溶剂中辐照一系列9 H-芴醇和9 H，9'H-联芴基，得到由其相应的9 H-芴基自由基衍生的光产物。通过激光闪光光解法直接观察到这些瞬态物质，并将其紫外/可见光谱与其相应阳离子的光谱进行比较。这些中间体的理论计算（密度泛函理论[DFT]）表明，它们的不稳定性质与相应阳离子的抗芳烃特征相似。