(α-Chlorobenzylidene)fluorene | 86457-77-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: (α-Chlorobenzylidene)fluorene
• 英文别名: 9-(α-chloro-benzylidene)-fluorene；9-(α-Chlor-benzyliden)-fluoren；β-Chlor-β-phenyl-α,α-biphenylen-ethylen；β-Chlor-β-phenyl-α,α-diphenylen-ethylen；9-<α-Chlor-benzyliden>-fluoren；9-(Alpha-chlorobenzylidene)fluorene；9-[chloro(phenyl)methylidene]fluorene
• CAS: 86457-77-4
• 化学式: C₂₀H₁₃Cl
• 分子量: 288.776
• InChiKey: BIHPCWNKBDTFRL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (α-Chlorobenzylidene)fluorene 以 乙腈 为溶剂， 生成 、
  参考文献：
  名称：

  Photochemical Formation and Electrophilic Reactivities of Vinyl Cations. Influence of Substituents, Anionic Leaving Groups, Solvents, and Excitation Wavelength on Photoheterolysis and Photohomolysis of 1-(p-R-Phenyl)-2-(2,2'-biphenyldiyl)vinyl Halides

  摘要：

  Using product analysis and time-resolved laser flash photolysis techniques, the photochemistry at lambda(exc) approximate to 250 and 310 nm (exe = excitation) of 1-(p-R-phenyl)-2-(2,2'-biphenyldiyl)vinyl halides (R = H, Me, MeO) in methanol and acetonitrile at room temperature was studied. The title compounds undergo photoheterolysis and photohomolysis to give vinyl cations =C+- (carbenium ions) and vinyl radicals =C-.-. The cation: radical ratio increases with electron-donating strength of the substituent R, H < Me < MeO, and with anionic leaving group power of the halide, F- < Cl- < Br- < I-, indicating that the cleavage of the C-X bond to yield cation and halide anion proceeds, in the rate-determining step, by heterolysis and not by homolysis followed by electron transfer in the radical pair. The cation:radical ratio is solvent dependent: e.g., for the vinyl bromide with R = MeO and with lambda(exc) = 308 nm, in CH2Cl2 as solvent, only radical is observed, in comparison with only cation in the much more polar solvent acetonitrile. In acetonitrile-methanol mixtures, the absolute yields of both cation and radical go through a maximum as the methanol content is increased, however, the cation:radical ratio decreases continuously with increasing [MeOH]. For a particular R, the quantum yield for C-X bond cleavage is higher at approximate to 250 than at approximate to 310 nm. Also, the cation:radical ratio is wavelength-dependent: at lambda(exc) approximate to 310 nm there is relatively more heterolysis than at lambda(exc),,, x 250 nm. Rate constants for reaction of the cations with nucleophiles were determined in acetonitrile. Those for reaction of the cation with R = MeO (lifetime in acetonitrile 7 ys) with anionic nucleophiles such as the halides are at the diffusion limit in this solvent, approximate to 2 x 10(10) M(-1) s(-1), whereas those for reaction with water, alcohols, and cyclic ethers are of the order 10(5)-10(6) M(-1) s(-1). The less stabilized cation (R = Me) reacts with alcohols faster by the factor approximate to 100, and it decays in acetonitrile approximate to 100 times more rapidly. Also, 1-(p-a-phenyl)-2-dimethylvinyl bromides (R = H, Me, MeO) were photolyzed in acetonitrile. In the case of R = MeO, the cation p-CH3O-C6H4-C+=CMe(2) was seen (lifetime 770 ns), and its reactivity with alcohols (k values of 10(6)-10(7) M(-1) s(-1)) and halides (k values of 10(10) M(-1) s(-1)) was determined. The vinyl radicals =C-.- react with O-2 to yield vinylperoxyl radicals =C-O-2(.) which have absorption maxima at approximate to 390 nm.

  DOI：

  10.1021/j100089a027
• 作为产物：
  描述：

  苯甲基膦酸二甲酯 在 叔丁基锂 作用下， 反应 0.5h， 生成 (α-Chlorobenzylidene)fluorene
  参考文献：
  名称：

  Synthesis with .alpha.-heterosubstituted phosphonates. Part 13. Synthesis of trisubstituted vinyl chlorides

  摘要：

  DOI：

  10.1021/jo00164a036

文献信息

• Kuhn,R. et al., Justus Liebigs Annalen der Chemie, 1962, vol. 654, p. 64 - 81
  作者：Kuhn,R. et al.

  DOI：——

  日期：——
• Staudinger; Siegwart, Helvetica Chimica Acta, 1920, vol. 3, p. 838
  作者：Staudinger、Siegwart

  DOI：——

  日期：——
• Reimlinger,H., Chemische Berichte, 1964, vol. 97, p. 339 - 348
  作者：Reimlinger,H.

  DOI：——

  日期：——
• Synthesis with .alpha.-heterosubstituted phosphonates. Part 13. Synthesis of trisubstituted vinyl chlorides
  作者：Michael D. Crenshaw、Hans Zimmer

  DOI：10.1021/jo00164a036

  日期：1983.8
• Photochemical Formation and Electrophilic Reactivities of Vinyl Cations. Influence of Substituents, Anionic Leaving Groups, Solvents, and Excitation Wavelength on Photoheterolysis and Photohomolysis of 1-(p-R-Phenyl)-2-(2,2'-biphenyldiyl)vinyl Halides
  作者：Jan-Maarten Verbeek、Marion Stapper、Erik S. Krijnen、Jan-Dirk van Loon、Gerrit Lodder、Steen Steenken

  DOI：10.1021/j100089a027

  日期：1994.9

  Using product analysis and time-resolved laser flash photolysis techniques, the photochemistry at lambda(exc) approximate to 250 and 310 nm (exe = excitation) of 1-(p-R-phenyl)-2-(2,2'-biphenyldiyl)vinyl halides (R = H, Me, MeO) in methanol and acetonitrile at room temperature was studied. The title compounds undergo photoheterolysis and photohomolysis to give vinyl cations =C+- (carbenium ions) and vinyl radicals =C-.-. The cation: radical ratio increases with electron-donating strength of the substituent R, H < Me < MeO, and with anionic leaving group power of the halide, F- < Cl- < Br- < I-, indicating that the cleavage of the C-X bond to yield cation and halide anion proceeds, in the rate-determining step, by heterolysis and not by homolysis followed by electron transfer in the radical pair. The cation:radical ratio is solvent dependent: e.g., for the vinyl bromide with R = MeO and with lambda(exc) = 308 nm, in CH2Cl2 as solvent, only radical is observed, in comparison with only cation in the much more polar solvent acetonitrile. In acetonitrile-methanol mixtures, the absolute yields of both cation and radical go through a maximum as the methanol content is increased, however, the cation:radical ratio decreases continuously with increasing [MeOH]. For a particular R, the quantum yield for C-X bond cleavage is higher at approximate to 250 than at approximate to 310 nm. Also, the cation:radical ratio is wavelength-dependent: at lambda(exc) approximate to 310 nm there is relatively more heterolysis than at lambda(exc),,, x 250 nm. Rate constants for reaction of the cations with nucleophiles were determined in acetonitrile. Those for reaction of the cation with R = MeO (lifetime in acetonitrile 7 ys) with anionic nucleophiles such as the halides are at the diffusion limit in this solvent, approximate to 2 x 10(10) M(-1) s(-1), whereas those for reaction with water, alcohols, and cyclic ethers are of the order 10(5)-10(6) M(-1) s(-1). The less stabilized cation (R = Me) reacts with alcohols faster by the factor approximate to 100, and it decays in acetonitrile approximate to 100 times more rapidly. Also, 1-(p-a-phenyl)-2-dimethylvinyl bromides (R = H, Me, MeO) were photolyzed in acetonitrile. In the case of R = MeO, the cation p-CH3O-C6H4-C+=CMe(2) was seen (lifetime 770 ns), and its reactivity with alcohols (k values of 10(6)-10(7) M(-1) s(-1)) and halides (k values of 10(10) M(-1) s(-1)) was determined. The vinyl radicals =C-.- react with O-2 to yield vinylperoxyl radicals =C-O-2(.) which have absorption maxima at approximate to 390 nm.

表征谱图