13,13-dichloro-5,6,11,12-tetrahydro-7,10-dimethoxy-5a,11a-methano-2-naphthacenecarbaldehyde | 265991-09-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: 13,13-dichloro-5,6,11,12-tetrahydro-7,10-dimethoxy-5a,11a-methano-2-naphthacenecarbaldehyde
• CAS: 265991-09-1
• 化学式: C₂₂H₂₀Cl₂O₃
• 分子量: 403.305
• InChiKey: GRWOLCSHGHWFCR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.57
• 重原子数：
  27.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  8,12-diethyl-2,3,7,13,17,18-hexamethyl-a,c-biladiene dihydrobromide 、 13,13-dichloro-5,6,11,12-tetrahydro-7,10-dimethoxy-5a,11a-methano-2-naphthacenecarbaldehyde 在 氢溴酸 作用下， 以 甲醇 、 溶剂黄146 为溶剂， 反应 24.0h， 以29.8%的产率得到5-(13,13-dichloro-5,6,11,12-tetrahydro-1,4-dimethoxy-5a,11a-methano-8-naphthacenyl)-13,17-diethyl-2,3,7,8,12,18-hexamethyl-21H,23H-porphine
  参考文献：
  名称：

  Large Acceleration Effect of Photoinduced Electron Transfer in Porphyrin−Quinone Dyads with a Rigid Spacer Involving a Dihalosubstituted Three-Membered Ring

  摘要：

  To understand the contribution of spacer structure toward electron transfer (ET) and to regulate electronic coupling between a redox pair, porphyrin-spacer-benzoquinone molecules were prepared where spacers are trans-decalin and dihalosubstituted tricyclo[4.4.1.0]undecane including a three-membered ring. These compounds were designed to have almost the same separation distance between a redox pair, the same number of intervening bonds, and the nearly equal free energy change associated with the ET reaction. The ET rates for the charge separation process were evaluated on the basis of the fluorescence lifetimes. A quite large difference in the ET rates was observed among these compounds, and the ET rates for the compounds having the three-membered rings were ca. 50 to 60 times larger than that with trans-decalin spacer in THF. From the analysis of temperature dependence of the ET rates, it was shown that the observed rate acceleration is caused by both an increase of the electronic coupling and a decrease of the reorganization energy, Ab initio calculations of the electronic coupling elements and on molecular orbitals for the cyclopropanes predicted that the former may be due to the enhancement of the ET pathways arising from the bent geometry of the spacer or of the mixing pathway induced by a very low lying antibonding orbital in the dihalosubstituted cyclopropane.

  DOI：

  10.1021/ja9900454
• 作为产物：
  描述：

  8-bromo-1,4-dimethoxy-5,6,11,12-tetrahydronaphthacene 在 正丁基锂 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.08h， 生成 13,13-dichloro-5,6,11,12-tetrahydro-7,10-dimethoxy-5a,11a-methano-2-naphthacenecarbaldehyde
  参考文献：
  名称：

  Large Acceleration Effect of Photoinduced Electron Transfer in Porphyrin−Quinone Dyads with a Rigid Spacer Involving a Dihalosubstituted Three-Membered Ring

  摘要：

  To understand the contribution of spacer structure toward electron transfer (ET) and to regulate electronic coupling between a redox pair, porphyrin-spacer-benzoquinone molecules were prepared where spacers are trans-decalin and dihalosubstituted tricyclo[4.4.1.0]undecane including a three-membered ring. These compounds were designed to have almost the same separation distance between a redox pair, the same number of intervening bonds, and the nearly equal free energy change associated with the ET reaction. The ET rates for the charge separation process were evaluated on the basis of the fluorescence lifetimes. A quite large difference in the ET rates was observed among these compounds, and the ET rates for the compounds having the three-membered rings were ca. 50 to 60 times larger than that with trans-decalin spacer in THF. From the analysis of temperature dependence of the ET rates, it was shown that the observed rate acceleration is caused by both an increase of the electronic coupling and a decrease of the reorganization energy, Ab initio calculations of the electronic coupling elements and on molecular orbitals for the cyclopropanes predicted that the former may be due to the enhancement of the ET pathways arising from the bent geometry of the spacer or of the mixing pathway induced by a very low lying antibonding orbital in the dihalosubstituted cyclopropane.

  DOI：

  10.1021/ja9900454