3,10-dimethoxypentacyclo[10.2.2.15,8.02,11.04,9]heptadeca-2,4(9),10,13-tetraene | 157870-35-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: 3,10-dimethoxypentacyclo[10.2.2.15,8.02,11.04,9]heptadeca-2,4(9),10,13-tetraene
• CAS: 157870-35-4
• 化学式: C₁₉H₂₂O₂
• 分子量: 282.382
• InChiKey: FNTRYUXDRBYCJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.58
• 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：

  3,10-dimethoxypentacyclo[10.2.2.15,8.02,11.04,9]heptadeca-2,4(9),10,13-tetraene 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 、 乙酸乙酯 为溶剂， 25.0 ℃ 、551.58 kPa 条件下， 反应 3.0h， 以100%的产率得到9,10-Dimethoxy-1,4-ethano-5,8-methano-1,2,3,4,5,6,7,8-octahydroanthracene
  参考文献：
  名称：

  Isolation of Novel Radical Cations from Hydroquinone Ethers. Conformational Transition of the Methoxy Group upon Electron Transfer

  摘要：

  Hydroquinone ethers as the bis-annulated derivatives R1-R3 are excellent electron donors by virtue of the facile oxidation to their radical cations R1(.+), R2(.-), and R3(.-) that are readily isolable as unusually robust SbCl6- and BF4- salts persistent in air for prolonged periods. Although the gas-phase vertical ionization potentials of the methyl ethers R1a and R2a are the same (IP = 7.83 +/- 0.01 eV), the oxidation potential of R1a in dichloromethane solution is less positive than that of R2a (E(1/2) = 1.11 and 1.30 V, respectively). The significantly lower value of E(1/2) for R1a relative to R2a, despite minimal changes in structure, is attributed to the conformational change that can occur in the radical cation. Indeed, X-ray crystallographic analysis of R1a, R2a, and R1a(.-) shows that the increased donor strength of R1a is derived from the enhanced (resonance) stabilization of R1a(.-), in which the methoxy group undergoes a 90 degrees rotation to the favorable coplanar conformation with respect to the aromatic ring. The subtle variation in the molecular structures of R1 and R2 accounts for the difference in nonbonded steric effects arising from the bridgehead alpha-hydrogens toward the methoxy groups.

  DOI：

  10.1021/jo00119a017
• 作为产物：
  描述：

  pentacyclo[10.2.2.15,8.02,11.04,9]heptadeca-4(9),13-diene-3,10-dione 、 碘甲烷 在 sodium ethanolate 作用下， 以 乙醇 为溶剂， 以90%的产率得到3,10-dimethoxypentacyclo[10.2.2.15,8.02,11.04,9]heptadeca-2,4(9),10,13-tetraene
  参考文献：
  名称：

  Isolation of Novel Radical Cations from Hydroquinone Ethers. Conformational Transition of the Methoxy Group upon Electron Transfer

  摘要：

  Hydroquinone ethers as the bis-annulated derivatives R1-R3 are excellent electron donors by virtue of the facile oxidation to their radical cations R1(.+), R2(.-), and R3(.-) that are readily isolable as unusually robust SbCl6- and BF4- salts persistent in air for prolonged periods. Although the gas-phase vertical ionization potentials of the methyl ethers R1a and R2a are the same (IP = 7.83 +/- 0.01 eV), the oxidation potential of R1a in dichloromethane solution is less positive than that of R2a (E(1/2) = 1.11 and 1.30 V, respectively). The significantly lower value of E(1/2) for R1a relative to R2a, despite minimal changes in structure, is attributed to the conformational change that can occur in the radical cation. Indeed, X-ray crystallographic analysis of R1a, R2a, and R1a(.-) shows that the increased donor strength of R1a is derived from the enhanced (resonance) stabilization of R1a(.-), in which the methoxy group undergoes a 90 degrees rotation to the favorable coplanar conformation with respect to the aromatic ring. The subtle variation in the molecular structures of R1 and R2 accounts for the difference in nonbonded steric effects arising from the bridgehead alpha-hydrogens toward the methoxy groups.

  DOI：

  10.1021/jo00119a017

文献信息

• Rathore, Rajendra; Bosch, Eric; Kochi, Jay K., Journal of the Chemical Society. Perkin transactions II, 1994, # 6, p. 1157 - 1166
  作者：Rathore, Rajendra、Bosch, Eric、Kochi, Jay K.

  DOI：——

  日期：——
• Rathore Rajendra, Bosch Eric, Kochi Jay K., J. Chem. Soc. Perkin Trans. 2, (1994) N 6, S 1157- 1166
  作者：Rathore Rajendra, Bosch Eric, Kochi Jay K.

  DOI：——

  日期：——