(1R,2R,5S,6S)-3,8-Dimethyl-4,7-diphenyl-tricyclo[4.2.2.02,5]deca-3,7-diene | 61109-78-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1R,2R,5S,6S)-3,8-Dimethyl-4,7-diphenyl-tricyclo[4.2.2.02,5]deca-3,7-diene
• CAS: 61109-78-2
• 化学式: C₂₄H₂₄
• 分子量: 312.455
• InChiKey: OZALZEYDTDQCML-HBUYNFGHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.22
• 重原子数：
  24.0
• 可旋转键数：
  2.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  (1R,2R,5S,6S)-3,8-Dimethyl-4,7-diphenyl-tricyclo[4.2.2.02,5]deca-3,7-diene 以 乙醚 为溶剂， 反应 2.0h， 生成 2,5-dimethyl-3,4-diphenylpentacyclo[4.4.0.02,5.03,8.04,7]decane
  参考文献：
  名称：

  Photosensitized [2+2] cycloreversion reactions of arylated cage compounds in nonpolar solvents. Highly efficient adiabatic exciplex isomerization

  摘要：

  Photosensitized [2+2] cycloreversion reactions of arylated cage compounds 1 to dienes 2 using several cyanoaromatics as sensitizers are reported. In acetonitrile, 1a isomerized to 2a via an efficient cation-radical chain process. In contrast, the isomerization of 1a to 2a proceeded via an exciplex in benzene. Interestingly, the exciplex emission maximum observed in the fluorescence quenching by 1a was the same as that by 2a. Such a coincidence was also observed in a series of arylated cage compounds 1a-d and dienes 2a-d in various solvents. These observations together with the results obtained from reaction and exciplex emission quenching experiments clearly demonstrated the occurrence of adiabatic exciplex isomerization of 1 to 2. Efficiencies (A(e)) of the adiabatic process obtained by comparing the intensities of the observed exciplex emissions with those of diene exciplex emissions were quite high and became almost quantitative in some cases. A(e) values were found to increase as (1) the oxidation potentials (E1/2ox) of cage compounds 1a-d decreased, (2) the reduction potentials (E1/2red) of sensitizers increased, and (3) the solvent polarity (E(T)) increased.

  DOI：

  10.1021/jo00006a039
• 作为产物：
  描述：

  在 9,10-Dicyanophenanthren 作用下， 以 苯 为溶剂， 生成 (1R,2R,5S,6S)-3,8-Dimethyl-4,7-diphenyl-tricyclo[4.2.2.02,5]deca-3,7-diene
  参考文献：
  名称：

  Organic photochemistry. 68. Exciplex isomerization in photosensitized cycloreversion reactions of cage compounds

  摘要：

  DOI：

  10.1021/ja00334a070

文献信息

• Quantum Amplified Isomerization:  A New Concept for Polymeric Optical Materials
  作者：J. G. Gillmore、J. D. Neiser、K. A. McManus、Y. Roh、G. W. Dombrowski、T. G. Brown、J. P. Dinnocenzo、S. Farid、D. R. Robello

  DOI：10.1021/ma050348k

  日期：2005.9.1

  quantum amplified isomerization (QAI). The QAI process utilizes photoinitiated, cation radical isomerization chemistry in a polymeric medium. Two classes of materials are described:  one where the QAI reactant is molecularly doped in the polymer matrix and another where the reactant is part of a functionalized polymer. Quantum yield experiments demonstrate that the isomerization reaction can proceed by

  在称为量子放大异构化（QAI）的过程的基础上描述了新型光敏聚合物的制备和评估。QAI工艺在聚合物介质中利用了光引发的阳离子自由基异构化化学反应。描述了两类材料：一种是QAI反应物分子掺杂在聚合物基质中，另一种是反应物是功能化聚合物的一部分。量子产率实验表明，异构化反应可以通过链式工艺以中等效率进行。光化学转化实验表明，QAI反应物的高度转化是可能的。转化率和程度与聚合物的玻璃化转变温度密切相关。对于分子掺杂的聚合物，检验并排除了基于反应物的扩散或相分离来解释高转化率的假说。讨论了模型以合理化影响量子产率和光化学转化的实验因素。
• Cycloreversion Reaction of Cage Compounds Initiated by Aminium Cation Radical Salts
  作者：Eietsu Hasegawa、Toshio Mukai

  DOI：10.1246/bcsj.58.3391

  日期：1985.11

  with triarylaminium cation radical salts, 3 and 4, resulted in the effective conversion of 1 to dienes 2. The cation radical isomerization induced by electron-transfer from 1 to aminium salt was suggested by the effect of substituent of 1 as well as by the effect of addition of electron donors as quenchers.

  用三芳基胺阳离子自由基盐 3 和 4 处理笼状化合物 1 导致 1 有效转化为二烯 2。 1 取代基的影响也表明了由 1 到胺盐的电子转移引起的阳离子自由基异构化由于添加电子供体作为猝灭剂的作用。
• ELECTRODE-CATALYZED [2+2]CYCLOREVERSION REACTION OF PHENYLATED BIS-HOMOCUBANES
  作者：Yasutake Takahashi、Katsuhiro Sato、Tsutomu Miyashi、Toshio Mukai

  DOI：10.1246/cl.1984.1553

  日期：1984.9.5

  The constant potential anodic oxidation reaction of phenylated bis-homocubanes involved the [2+2]cycloreversion to give the dienes via a radical chain mechanism.

  苯基化双高立方烷的恒电位阳极氧化反应涉及 [2+2] 环转化，通过自由基链机制得到二烯。
• METAL-CATALYZED REARRANGEMENT OF PHENYLATED BIS-HOMOCUBANE
  作者：Kinichi Yokoyama、Yumi Saegusa、Tsutomu Miyashi、Chizuko Kabuto、Toshio Mukai

  DOI：10.1246/cl.1984.89

  日期：1984.1.5

  The reaction of the phenylated bis-homocubane with Fe(III) exclusively afforded the [2+2]cycloreversion product (6), whereas that with Ag(I) gave 6 together with the skeletal rearranged snoutane derivative.

  苯基化双高立方烷与 Fe(III) 的反应完全提供了 [2+2] 环转化产物 (6)，而与 Ag(I) 的反应与骨架重排的鼻子衍生物一起得到了 6。
• Reaction mechanism of a pyrylium salt-sensitised photocycloreversion of a cage molecule
  作者：Keiji Okada、Kunio Hisamitsu、Tsutomu Miyashi、Toshio Mukai

  DOI：10.1039/c39820000974

  日期：——

  The pyrylium salt-sensisted photocycloreversion of a cage molecule (1) was studied in terms of the effects of the concentration of (1), of light intensity, and of a quencher (tetramethoxybenzene), to confirm the mechanism as an electron transfer radical ion chain process.

  一个笼分子的吡喃鎓盐sensisted photocycloreversion（1）中的浓度的影响方面进行了研究（1），光强度和淬灭剂（基苯）的，以确认机构作为电子转移自由基离子连锁过程。