5,5-dimethyl-4,6-diphenyl-2,3,3a,6a-tetrahydro-1H-pentalen-4-ylium-6-ide | 182162-47-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 5,5-dimethyl-4,6-diphenyl-2,3,3a,6a-tetrahydro-1H-pentalen-4-ylium-6-ide
• CAS: 182162-47-6
• 化学式: C₂₂H₂₄
• 分子量: 288.433
• InChiKey: CQZBSZZQLTWLDZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5,5-dimethyl-4,6-diphenyl-2,3,3a,6a-tetrahydro-1H-pentalen-4-ylium-6-ide 以 苯 为溶剂， 生成 housane
  参考文献：
  名称：

  1,3-环戊二基双自由基：三重-单重系统间交叉的取代基和温度依赖性

  摘要：

  33 1,3-二芳基-1,3-环戊二基三线态双自由基的寿命由相应偶氮烷前体的激光闪光光解确定。在 294 K 的脱气溶液中，一阶衰减率常数的范围为 0.8 到 16.7 × 105 s-1，并且表现出对布朗 σ+ 取代基常数的系统但非线性的依赖性。根据双轨道中的双电子模型对自旋轨道耦合的分析表明，电子对系统间交叉率的影响是通过影响双自由基最低单线态波函数中离子贡献的权重来实现的。与直觉相反，但与模型的预测一致，推挽取代不会增强离子贡献。Arrhenius 参数，Ea = 2−6 kcal mol-1 和 A = 107−1010 s-1，由衰减率常数的温度依赖性确定。使用敏感的统计测试来确定 Arrhenius 参数表现出焓-熵补偿，...

  DOI：

  10.1021/ja991362d
• 作为产物：
  描述：

  (1α,4α,4aα,7aα)-4,4a,5,6,7,7a-Hexahydro-8,8-dimethyl-1,4-diphenyl-1,4-methano-1H-cyclopenta[d]pyridazin 在 2-甲基四氢呋喃 作用下， 以 solid matrix 为溶剂， 生成 5,5-dimethyl-4,6-diphenyl-2,3,3a,6a-tetrahydro-1H-pentalen-4-ylium-6-ide
  参考文献：
  名称：

  光化学生成的环戊烷-1,3-二基三重基双自由基作为模型系统，用于通过EPR SpectrumD参数评估杂芳基取代的苄基单自由基的自旋离域

  摘要：

  在2-MTHF玻璃基质中，在77 K的温度下测定了环戊烷-1,3-二基三线态双自由基2的零场D参数。发现D值与杂芳基取代基的顺序递减有关，顺序为3-呋喃基>3-噻吩基>4-吡啶基≈3-N-氧代吡啶基>2-吡啶基≈3-吡啶鎓>3-吡啶鎓≈苯基2-吡啶鎓4-吡啶鎓2-呋喃基2-噻吩基4-N-氧代吡啶基。对于苄基单自由基4，与已报道的aα偶合常数（r2 = 0.953）具有良好的线性相关性；对于枯基单自由基3，与半经验计算（PM3）的α自旋密度（r2 = 0.928）具有良好的线性相关性。为了合理化观察到的电子效应，为了方便起见，将ΔDAr量表定义为不同杂芳基取代基相对于苯基的自旋非局域能力的量度，以苯基

  DOI：

  10.1039/a607513d

文献信息

• Adam, Waldemar; Van Barneveld, Claus; Emmert, Oliver, Journal of the Chemical Society. Perkin Transactions 2 (2001), 2000, # 4, p. 637 - 641
  作者：Adam, Waldemar、Van Barneveld, Claus、Emmert, Oliver

  DOI：——

  日期：——
• Wavelength-Selective Photodenitrogenation of Azoalkanes to High-Spin Polyradicals with Cyclopentane-1,3-diyl Spin-Carrying Units and Their Photobleaching:  EPR/UV Spectroscopy and Product Studies of the Matrix-Isolated Species
  作者：Waldemar Adam、Wiebke Maas、Werner M. Nau

  DOI：10.1021/jo0013960

  日期：2000.12.1

  The photolysis of the mono-, bis-, and trisazoalkanes 1, 2, and 3 in a toluene matrix at 77 K has been studied by EPR and UV spectroscopy. The purpose was to find the optimal conditions for the generation of the corresponding organic high-spin polyradicals (the triplet diradicals D-1, D-2, and D-3, the tetraradicals T-2 and T-3, and the hexaradical H-3) all with localized cyclopentane-1,3-diyl spin-carrying units, connected by m-phenylene (except D-1) as ferromagnetic coupler. Irradiation of these azoalkanes at 333, 351, or 364 nm gave different polyradical compositions. This observed wavelength dependence is due to the secondary photoreaction (photobleaching) of the polyradical intermediate. The photobleaching process has been examined in detail for the triplet diradical D-1, for which pi,pi* excitation affords the cyclopentenes 5 instead of the housane 4 (the usual product of the diradical D-1 on warm-up of the matrix). The pi,pi*,-excited diradical D-1 fragments into a pair of allyl and methyl radicals (the latter was observed by EPR spectroscopy of a photobleached sample), and recombination affords the cyclopentene. Similar photochemical events are proposed for the photobleaching of the tetraradical T-2 and hexaradicaI H-3, derived from the respective azoalkanes 2 and 3. Thus, photobleaching of the polyradicals competes effectively with their photogeneration from the azoalkane. This unavoidable event is the consequence of spectral overlap between the cumyl-radical pi,pi* chromophore of the polyradical and the n,pi*: chromophore of the azoalkane at the wavelength (364 MI), at which the latter is photoactive for the required extrusion of molecular nitrogen.