9-(α-bromo-α-p-methoxyphenylmethylene)fluorene | 33686-67-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 9-(α-bromo-α-p-methoxyphenylmethylene)fluorene
• 英文别名: 9-[Bromo-(4-methoxyphenyl)methylidene]fluorene
• CAS: 33686-67-8
• 化学式: C₂₁H₁₅BrO
• 分子量: 363.253
• InChiKey: FWYLBOJLXQQILU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  9-(α-bromo-α-p-methoxyphenylmethylene)fluorene 在 sodium ethanolate 、 溶剂黄146 作用下， 生成 9-Anisoylfluoren
  参考文献：
  名称：

  Vinylic cations from solvolysis. X. SN1 and nucleophilic addition-elimination routes for 9-(.alpha.-haloarylidene)fluorenes

  摘要：

  DOI：

  10.1021/jo00973a021
• 作为产物：
  描述：

  p-methoxybenzylidene fluorene 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 氯仿 为溶剂， 生成 9-(α-bromo-α-p-methoxyphenylmethylene)fluorene
  参考文献：
  名称：

  Abdou, Sadek E.; Habashy, Adiba; Aziz, Gamil, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1981, vol. 20, # 9, p. 755 - 758

  摘要：

  DOI：

文献信息

• Light-Induced Intramolecular Iodine-Atom Transfer Radical Addition of Alkyne: An Approach from Aryl Iodide to Alkenyl Iodide
  作者：Yanbin Zhang、Jincheng Xu、Hao Guo

  DOI：10.1021/acs.orglett.9b03519

  日期：2019.11.15

  reported toward iodine-substituted fluorene derivatives. A thioxanthone derivative was employed as a visible light sensitizer for this 5-exo-dig exclusive radical addition, and the newly formed vinyl iodide compounds were further proved to be effective partners for several cross-coupling reactions.

  据报道，光诱导的分子内碘原子转移自由基向碘取代的芴衍生物的添加。噻吨酮衍生物被用作该5-exo-dig排他性自由基加成的可见光敏化剂，并且新形成的乙烯基碘化物被进一步证明是几种交叉偶联反应的有效伴侣。
• Characterization of the excited-state reactivity of a persistent aryl-substituted allyl free radical
  作者：David T. Breslin、Marye Anne Fox

  DOI：10.1021/j100152a045

  日期：1993.12

  A family of stable aryl-substituted allyl radicals 1 (9H-fluoren-9-yl-9-[9H-fluroren]-9-ylidenephenylmethyls) has been characterized by electronic absorption spectroscopy, semiempirical (AM 1) molecular orbital calculations, and cyclic voltammetry. Photolysis of 1a in aerated solvents that are poorer hydrogen atom sources than toluene resulted in oxygenation (phi(OX) approximately 5 X 10(-4)) and cleavage products. A thermally reversible photocyclization mechanism is proposed to explain the oxygenation of 1a in inert solvents. Enhanced excited-state reactivity toward hydrogen and halogen atom donors was observed during the steady-state photolysis of 1a. Electron transfer from naphthalene to an excited state of 1a produces an extremely short lived (< 30 ps) 1a anion/naphthalene radical cation geminate pair.
• �ber substituierte Bis-biphenylen-allyl-Radikale
  作者：Richard Kuhn、Alfred Neugebauer

  DOI：10.1007/bf00909246

  日期：——
• 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.
• Amatore, Christian; Galli, Carlo; Gentili, Patrizia, Journal of the Chemical Society. Perkin transactions II, 1995, # 12, p. 2341 - 2350
  作者：Amatore, Christian、Galli, Carlo、Gentili, Patrizia、Guarnieri, Alessandra、Schottland, Ettie、Rappoport, Zvi

  DOI：——

  日期：——