9-(2,2-dimethylpropyl)-9-phenylfluorene

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 9-(2,2-dimethylpropyl)-9-phenylfluorene
• 英文别名: 9-(2,2-Dimethylpropyl)-9-phenylfluorene
• 化学式: C₂₄H₂₄
• 分子量: 312.455
• InChiKey: YKCOQGXNYBKLSO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  新戊基碘 、 9-苯基芴 在 正丁基锂 作用下， 生成 9-(2,2-dimethylpropyl)-9-phenylfluorene
  参考文献：
  名称：

  A Photochemical Probe for Single Electron Transfer in Nucleophilic Aliphatic Substitution: Evidence for Geminate Radical Coupling in the Solvent Cage

  摘要：

  A major effort to establish single electron transfer (SET) as an important pathway in nucleophilic aliphatic subsitution reactions has involved the use of cyclizable probes, e.g., 6-iodo-5,5-dimethyl-1-hexene. In order to examine the partition between cyclization and direct radical-radical recombination, we have investigated the ground-state and excited-state chemistry of the 9-phenylfluorenyl anion (9PF(-)) with neopentyl-type iodides. It has been shown that 9PF(-) does not react with Me(3)CCH(2)I, but it does undergo efficient reaction upon irradiation (Phi = 1.0) to yield nucleophilic aliphatic substitution products, With the sterically analogous cyclizable probe 6-iodo-5,5-dimethyl-1-hexene, no ground-state reaction is observed, However, both cyclized and uncyclized products of substitution, 9PFR(c) and 9PFR(u), are produced upon irradiation. Thus photoproducts clearly involving electron-transfer-induced radical intermediates can result without acommpanying free-radical cyclization. These results suggest that, although the observation of cyclized products in the reaction of a cyclizable radical probe with a nucleophile is evidence of a radical intermediate, the absence of such cyclized products does not require the absence of radical intermediates.

  DOI：

  10.1021/ja00115a001

文献信息

• A Photochemical Probe for Single Electron Transfer in Nucleophilic Aliphatic Substitution: Evidence for Geminate Radical Coupling in the Solvent Cage
  作者：Laren M. Tolbert、Xiao-Jing Sun、E. C. Ashby

  DOI：10.1021/ja00115a001

  日期：1995.3

  A major effort to establish single electron transfer (SET) as an important pathway in nucleophilic aliphatic subsitution reactions has involved the use of cyclizable probes, e.g., 6-iodo-5,5-dimethyl-1-hexene. In order to examine the partition between cyclization and direct radical-radical recombination, we have investigated the ground-state and excited-state chemistry of the 9-phenylfluorenyl anion (9PF(-)) with neopentyl-type iodides. It has been shown that 9PF(-) does not react with Me(3)CCH(2)I, but it does undergo efficient reaction upon irradiation (Phi = 1.0) to yield nucleophilic aliphatic substitution products, With the sterically analogous cyclizable probe 6-iodo-5,5-dimethyl-1-hexene, no ground-state reaction is observed, However, both cyclized and uncyclized products of substitution, 9PFR(c) and 9PFR(u), are produced upon irradiation. Thus photoproducts clearly involving electron-transfer-induced radical intermediates can result without acommpanying free-radical cyclization. These results suggest that, although the observation of cyclized products in the reaction of a cyclizable radical probe with a nucleophile is evidence of a radical intermediate, the absence of such cyclized products does not require the absence of radical intermediates.