2,3-bis(4-methoxyphenyl)bicyclo[2.2.2]oct-2-ene | 180578-71-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 2,3-bis(4-methoxyphenyl)bicyclo[2.2.2]oct-2-ene
• CAS: 180578-71-6
• 化学式: C₂₂H₂₄O₂
• 分子量: 320.431
• InChiKey: VUZCMSSYHIXUKB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,3-bis(4-methoxyphenyl)bicyclo[2.2.2]oct-2-ene 在 triethyloxonium hexachloroantimonate 作用下， 以 二氯甲烷 为溶剂， 以97%的产率得到2,3-bis(4-methoxyphenyl)bicyclo[2.2.2]oct-2-ene cation radical hexachloroantimonate
  参考文献：
  名称：

  结晶型芳族阳离子-自由基盐的制备和结构。六氯锑酸三乙基氧鎓作为新型（单电子）氧化剂。

  摘要：

  六氯锑酸三乙基氧鎓鎓盐[Et（3）O（+）SbCl（6）（-）]是芳香族供体（ArH）的选择性氧化剂，它可以方便地制备和分离结晶顺磁性盐[ArH（+）（*） ，SbCl（6）（-）]用于各种芳香族阳离子自由基的X射线结构测定。Meerwein盐[Et（3）O（+）SbCl（6）（-）]和纯路易斯酸氧化剂SbCl（5）之间的机理关系基于离子对内先前从氧到氯的乙基转移。

  DOI：

  10.1021/jo980407a
• 作为产物：
  描述：

  2,3-dibromobicyclo(2.2.2)oct-2-ene 、 4-甲氧基苯基溴化镁 在 bis-triphenylphosphine-palladium(II) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以94%的产率得到2,3-bis(4-methoxyphenyl)bicyclo[2.2.2]oct-2-ene
  参考文献：
  名称：

  Vicinal-diaryl interactions in stilbenoid hydrocarbons as observed in the through-space charge delocalization of their cation radicals

  摘要：

  在两类环替代的1,2-二苯基双环辛烷（stilbenoid）碳氢化合物1a-1d和2a-2c中，探测了邻位或1,2-苯基的构象偏好。UV-vis光谱揭示了，X射线晶体学证实了，stilbenoid 1a-1d中苯-苯相互作用的分子内（边缘对面）取向。最重要的是，当存在两对邻甲基取代基时，在X射线晶体学中建立了stilbenoid供体中的同面苯基团，并通过在阳离子自由基（2a+. -2c+.）中出现具有强吸收的新带，其λmax = 1100-1315 nm，类似于以前观察到的芳香族阳离子自由基的分子间（芳香族）相互作用。关键词：stilbenoid碳氢化合物，阳离子自由基，芳基-芳基相互作用。

  DOI：

  10.1139/v99-081

文献信息

• Preparation and Structures of Crystalline Aromatic Cation-Radical Salts. Triethyloxonium Hexachloroantimonate as a Novel (One-Electron) Oxidant
  作者：R. Rathore、A. S. Kumar、S. V. Lindeman、J. K. Kochi

  DOI：10.1021/jo980407a

  日期：1998.8.1

  Triethyloxonium hexachloroantimonate [Et(3)O(+)SbCl(6)(-)] is a selective oxidant of aromatic donors (ArH), and it allows the facile preparation and isolation of crystalline paramagnetic salts [ArH(+)(*), SbCl(6)(-)] for the X-ray structure determination of various aromatic cation radicals. The mechanistic relationship between the Meerwein salt [Et(3)O(+)SbCl(6)(-)] and the pure Lewis acid oxidant

  六氯锑酸三乙基氧鎓鎓盐[Et（3）O（+）SbCl（6）（-）]是芳香族供体（ArH）的选择性氧化剂，它可以方便地制备和分离结晶顺磁性盐[ArH（+）（*） ，SbCl（6）（-）]用于各种芳香族阳离子自由基的X射线结构测定。Meerwein盐[Et（3）O（+）SbCl（6）（-）]和纯路易斯酸氧化剂SbCl（5）之间的机理关系基于离子对内先前从氧到氯的乙基转移。
• Efficient Hydrogenation of Sterically Hindered Olefins with Borane−Methyl Sulfide Complex
  作者：R. Rathore、U. Weigand、J. K. Kochi

  DOI：10.1021/jo960357e

  日期：1996.1.1

  Sterically hindered olefins are efficiently reduced to the corresponding alkanes by the borane-methyl sulfide (BMS) complex at room temperature (or below) in dichloromethane containing a mild one-electron oxidant (such as an aromatic cation radical) or by the passage of an anodic current. In an alternative procedure, the hydrogenation of the same (electron-rich) olefins with the EMS complex (in the absence of a one-electron oxidant) is also carried out-in the presence of a strong Bronsted acid (such as HBF4). In the oxidative activation, olefin cation radicals are the first observable intermediates, and separate experiments (including transient electrochemistry) confirm the facile reduction of the olefin cation radical by borane to produce the corresponding alkane. The direct protonation of olefins produces carbocationic intermediates which are also efficiently reduced by borane to the corresponding alkanes. The intermediacy of both olefin cation radicals and carbocations in the hydrogenation procedure with borane is discussed.
• Potent Estrogen Receptor Ligands Based on Bisphenols with a Globular Hydrophobic Core
  作者：Yasuyuki Endo、Tomohiro Yoshimi、Kiminori Ohta、Tomoharu Suzuki、Shigeru Ohta

  DOI：10.1021/jm050195r

  日期：2005.6.1

  Candidate estrogen receptor (ER) ligands with two phenolic residues on a three-dimensional hydrophobic core structure (carborane, bicyclo[2.2.2]octene, or adamantane) were synthesized and biologically evaluated. The biological properties of the ligands were markedly dependent on the nature of the hydrophobic core structure. Bis(4-hydroxyphenyl)-o-carborane (6) was a partial agonist/antagonist for ER. 1,2Bis(4-hydroxyphenyl)bicyclo[2.2.2]octene (10) exhibited potent agonist activity for ER, even though the two phenolic groups are located similarly to those of 6.
• Vicinal-diaryl interactions in stilbenoid hydrocarbons as observed in the through-space charge delocalization of their cation radicals
  作者：Rajendra Rathore、Jay K Kochi

  DOI：10.1139/v99-081

  日期：1999.6.1

  The conformational preference of vicinal or 1,2-phenyl groups is probed in two classes of ring-substituted 1,2-diphenylbicyclooctene (stilbenoid) hydrocarbons 1a-1d and 2a-2c. UV-vis spectroscopy reveals, and X-ray crystallography verifies, the intramolecular (edge-to-face) orientation for the phenyl-phenyl interaction in stilbenoids 1a-1d. Most importantly, when two pairs of ortho-methyl substituents are present, the cofacial phenyl groups in the stilbenoid donors are established by X-ray crystallography and spectrally observed in the cation radicals (2a^+.-2c^+.) by the appearance of new bands with strong absorptions in the near IR with λ_max = 1100-1315 nm, analogous to those previously observed in intermolecular (aromatic) interactions of aromatic cation radicals.Key words: stilbenoid hydrocarbon, cation radical, aryl-aryl interaction.

  在两类环替代的1,2-二苯基双环辛烷（stilbenoid）碳氢化合物1a-1d和2a-2c中，探测了邻位或1,2-苯基的构象偏好。UV-vis光谱揭示了，X射线晶体学证实了，stilbenoid 1a-1d中苯-苯相互作用的分子内（边缘对面）取向。最重要的是，当存在两对邻甲基取代基时，在X射线晶体学中建立了stilbenoid供体中的同面苯基团，并通过在阳离子自由基（2a+. -2c+.）中出现具有强吸收的新带，其λmax = 1100-1315 nm，类似于以前观察到的芳香族阳离子自由基的分子间（芳香族）相互作用。关键词：stilbenoid碳氢化合物，阳离子自由基，芳基-芳基相互作用。