1-(芴-9-亚基)-1-甲氧基-1-苯基甲烷 | 27808-13-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1-(芴-9-亚基)-1-甲氧基-1-苯基甲烷
• 英文名称: 1-(Fluoren-9-ylidene)-1-methoxy-1-phenylmethane
• 英文别名: 9-(α-methoxybenzylidene)fluorene；9--fluoren；Methyl-oxy-1'-benzyliden-9-fluoren；9-[methoxy(phenyl)methylidene]fluorene
• CAS: 27808-13-5
• 化学式: C₂₁H₁₆O
• 分子量: 284.357
• InChiKey: OLOHDEDBLWGPGQ-UHFFFAOYSA-N

物化性质

• 沸点：
  431.6±24.0 °C(Predicted)
• 密度：
  1.173±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.23
• 重原子数：
  22.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  fluoren-9-yl-phenyl ketone 在 盐酸 、 对甲苯磺酸 作用下， 以 甲醇 为溶剂， 生成 1-(芴-9-亚基)-1-甲氧基-1-苯基甲烷
  参考文献：
  名称：

  Perz,R.; Boyer,J., Bulletin de la Societe Chimique de France, 1970, p. 262 - 267

  摘要：

  DOI：

文献信息

• Use of the Wadsworth–Emmons reaction for preparing hindered vinyl ethers and related 1,2-dioxetanes
  作者：Carl A. Roeschlaub、Peter G. Sammes

  DOI：10.1039/b002101f

  日期：——

  Arylaldehyde acetals can be reacted with trimethyl phosphite to produce the corresponding dimethyl α-methoxybenzylphosphonates, themselves used in a Wadsworth–Emmons reaction with adamantanone to produce hindered methyl vinyl ethers. These vinyl ethers are useful in the preparation of chemiluminescent 1,2-dioxetanes. The scope of the reaction has been explored.

  芳香醛缩醛可以与三甲基磷酸酯反应，生成相应的二甲基α-甲氧基苯基磷酸酯，这些磷酸酯可用于Wadsworth-Emmons反应，与亚当坦酮反应生成受阻的甲基乙烯醚。这些乙烯醚在制备化学发光的1,2-二噁烷中非常有用。反应的范围已被探索。
• Photolysis of the vinyl bromide 9-(α-bromobenzylidene)fluorene in methanol. Effect of wavelength of irradiation, sodium methoxide and oxygen
  作者：J.M. Verbeek、J. Cornelisse、G. Lodder

  DOI：10.1016/s0040-4020(01)88173-4

  日期：1986.1

  A quantitative study of the photosolvolysis of 9-(α-bromobenzylidene)fluorene (1) in methanol reveals that the wavelength of irradiation, the presence of sodium methoxide and the presence of oxygen strongly influence the product distribution and the quantum yields of the reaction.

  定量研究9-（α-溴亚苄基）芴（1）在甲醇中的光溶剂分解结果表明，辐照的波长，甲醇钠的存在和氧的存在强烈影响产物的分布和反应的量子产率。
• 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.