(1α,4α,4aα,7aα)-4,4a,5,6,7,7a-Hexahydro-8,8-dimethyl-1,4-diphenyl-1,4-methano-1H-cyclopenta[d]pyridazin | 105787-09-5

• 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: (1α,4α,4aα,7aα)-4,4a,5,6,7,7a-Hexahydro-8,8-dimethyl-1,4-diphenyl-1,4-methano-1H-cyclopenta[d]pyridazin
• 英文别名: (1S,2R,6S,7R)-10,10-dimethyl-1,7-diphenyl-8,9-diazatricyclo[5.2.1.02,6]dec-8-ene
• CAS: 105787-09-5
• 化学式: C₂₂H₂₄N₂
• 分子量: 316.446
• InChiKey: ZQXBLFLRNDMJDZ-ZIEJVCCYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  4,4-dimethyl-3,5-diphenyl-4H-pyrazole 在 palladium on activated charcoal Nafion H 、 氢气 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 24.0h， 生成 (1α,4α,4aα,7aα)-4,4a,5,6,7,7a-Hexahydro-8,8-dimethyl-1,4-diphenyl-1,4-methano-1H-cyclopenta[d]pyridazin
  参考文献：
  名称：

  Beck, Karin; Huenig, Siegfried, Chemische Berichte, 1987, vol. 120, p. 477 - 484

  摘要：

  DOI：

文献信息

• Diastereo- and Regioselective Synthesis of Diquinanes and Related Systems from Tricyclo[3.3.0.02,4]octanes by Chemical Electron Transfer (CET)
  作者：Waldemar Adam、Thomas Heidenfelder、Coskun Sahin

  DOI：10.1055/s-1995-4072

  日期：1995.9

  A new synthetic methodology for diquinanes by one-electron oxidation of tricyclo[3.3.0.02,4]octanes and subsequent stereocontrolled rearrangement is provided. The latter compounds are conveniently accessible through acid-catalyzed isopyrazole cycloaddition, followed by hydrogenation and photoextrusion of molecular nitrogen. The oxidative rearrangement of the tricyclooctanes proceeds catalytically and cleanly to afford regio- and diastereoselectively the corresponding diquinanes.

  提供了一种通过三环[3.3.0.02,4]辛烷的单电子氧化和随后的立体控制重排合成二喹烷的新合成方法。后者化合物可通过酸催化异吡唑环加成，随后氢化和分子氮的光排出方便地获得。三环辛烷的氧化重排催化且清洁地进行，区域和立体选择性地得到相应的二喹烷。
• The <i>D</i> Parameter (EPR Zero-Field Splitting) of Localized 1,3-Cyclopentanediyl Triplet Diradicals as a Measure of Electronic Substituent Effects on the Spin Densities in <i>Para</i>-Substituted Benzyl-Type Radicals
  作者：Waldemar Adam、Fumio Kita、Heinrich M. Harrer、Werner M. Nau、Rainer Zipf

  DOI：10.1021/jo960396q

  日期：1996.1.1

  parameter of the triplet diradical species. A theoretical analysis shows that the D parameter is a measure of the spin density rho at the benzylic positions and the inter-radical distance d in localized diradicals. A good correlation exists between the D parameter of these triplet diradicals (constant inter-radical distance d) and the EPR hyperfine coupling constants of the corresponding benzyl-type monoradicals

  这种可加性使我们能够将这些三重态双自由基看作是两个单独的单自由基组分的复合物，并使我们能够从三重态双自由基种类的D参数评估苄基型单自由基的有价值的电子性能。理论分析表明，D参数是对苄基位置的自旋密度rho和局部双基自由基的径向间距d的度量。这些三重双自由基的D参数（恒定的自由基间距d）与相应的苄基单自由基的EPR超精细偶合常数之间存在良好的相关性，这表明所观察到的电子取代基效应反映了C原子上自旋密度的变化。激进的网站。
• Preferred Formation ofanti-Housane (Retention) in the Sensitized Photodenitrogenation of Cyclopentane-Annellated DBH-Type Azoalkanes through Long-Range Steric Effects in the Cyclization of the Triplet Cyclopentane-1,3-diyl Diradicals
  作者：Waldemar Adam、Manfred Diedering、Vicente Martí

  DOI：10.1002/ejoc.200390098

  日期：2003.2

  The photolysis of the cyclopentene- and cyclopentane-annellated DBH-type azoalkanes 1a and 1b affords under singlet conditions (high-temperature direct photolysis) predominantly the inverted housanes syn-2 in similar amounts for both derivatives 2a and 2b. Under triplet conditions (low-temperature direct or benzophenone-sensitized photolysis), the photolysis leads to the retained housane anti-2 as

  环戊烯和环戊烷退火的 DBH 型偶氮烷烃 1a 和 1b 的光解在单线态条件下（高温直接光解）主要提供了衍生物 2a 和 2b 数量相似的反向 housanes syn-2。在三重态条件下（低温直接或二苯甲酮敏化光解），光解导致保留的 housane anti-2 作为主要的非对映异构体，但 2a 的顺/反 housane 比率存在显着差异（38:62）对于 2b (6:94)。三线态途径的抗立体选择性的这种显着差异在环戊烷-1,3-二基三线态双自由基 3DR 环化过程中，环化环和嵴二甲基取代的亚甲基桥之间的长程空间相互作用在机械上合理化在 ISC 之后。相比之下，对于单线态过程，中间二氮烯基双自由基 1DZ 沿 SH2 途径（反转）的脱氮对这些远程空间效应非常不敏感。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany,
• Photochemically generated cyclopentane-1,3-diyl triplet diradicals as model systems for the assessment of spin delocalization in heteroaryl-substituted benzyl-type monoradicals through the EPR spectral D parameter
  作者：Waldemar Adam、Oliver Emmert、Heinrich M. Harrer

  DOI：10.1039/a607513d

  日期：——

  The zero-field D parameters of a comprehensive set of cyclopentane-1,3-diyl triplet diradicals 2 were determined at 77 K in a 2-MTHF glass matrix. The D values were found to be dependent on the heteroaryl substituents in the decreasing order 3-furyl 3-thienyl > 4-pyridyl ≈ 3-N-oxypyridyl > 2-pyridyl ≈ 3-pyridylium > 3-pyridyl ≈ phenyl 2-pyridylium 4-pyridylium 2-furyl 2-thienyl 4-N-oxypyridyl. Good linear correlations were obtained with the reported aα coupling constants (r2 = 0.953) for the benzyl monoradicals 4 and with the semiempirically calculated (PM3) α spin densities (r2 = 0.928) for the cumyl monoradicals 3. To rationalize the observed electronic effects, for convenience the ΔDAr scale was defined as a measure of the spin-delocalizing ability of the different heteroaryl substituents relative to the phenyl group as reference. The hitherto unknown electronic effects of N-oxidation and protonation for the different pyridyl regioisomers as well as the regioisomeric effects of the furyl and thienyl substituents, are experimentally reflected accurately by the changes in the D parameter of the triplet diradicals 2 and explained theoretically with the help of MO calculations for the corresponding monoradicals 3.

  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
• Detection of Phenyl-Substituted Radical Cations Derived from Cyclopentyl- and Urazole-Type Azoalkanes by Pulse Radiolysis:  Influence of Heteroatom Substitution on the Radical Cation Reactivities
  作者：Waldemar Adam、Thomas Kammel、Marion Toubartz、Steen Steenken

  DOI：10.1021/ja970647s

  日期：1997.11.1

  The radical cations of cyclopentane- and urazole-annelated azoalkanes and housanes were generated by pulse radiolysis and the transients characterized spectrally and kinetically by time-resolved optical monitoring. For the bridgehead-substituted diphenyl derivatives of the cyclopentane-annelated azoalkane 1 and housane 2 only the corresponding proximate 1,2 radical cation species were observed, generated

  环戊烷和尿唑退火的偶氮烷烃和 housanes 的自由基阳离子是通过脉冲辐射分解产生的，瞬态通过时间分辨光学监测在光谱和动力学上表征。对于环戊烷退火的偶氮烷 1 和 housane 2 的桥头取代二苯基衍生物，仅观察到相应的近似 1,2 自由基阳离子物种，由最初形成且寿命太短 (<1 μs) 的不饱和 1,3 自由基产生阳离子通过 1,2-甲基迁移。相比之下，对于相应的 urazole-annelated 偶氮烷烃 4，检测到初始的 1,3 自由基阳离子 5•+，其中甲基取代的 5b•+ 去质子化为自由基 5b•。