(1α,4α,4aα,7aα)-4,4a,7,7a-Tetrahydro-8,8-dimethyl-1,4-diphenyl-1,4-methano-1H-cyclopenta[d]pyridazin | 105787-00-6

• 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: (1α,4α,4aα,7aα)-4,4a,7,7a-Tetrahydro-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]deca-3,8-diene
• CAS: 105787-00-6
• 化学式: C₂₂H₂₂N₂
• 分子量: 314.43
• InChiKey: BGGSPXOPIOYYOT-KIZRIRGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 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,7,7a-Tetrahydro-8,8-dimethyl-1,4-diphenyl-1,4-methano-1H-cyclopenta[d]pyridazin 在 三氟乙酸 作用下， 以 氘代氯仿 为溶剂， 生成 4,4-dimethyl-3,5-diphenyl-4H-pyrazole
  参考文献：
  名称：

  Electronic Substituent Effects on the Acid-Catalyzed [4+ + 2] Cycloaddition of Isopyrazoles with Cyclopentadiene and the Photochemical and Thermal Denitrogenation of the Resulting 1,4-Diaryl-7,7-dimethyl-2,3-diazabicyclo[2.2.1]hept-2-ene Azoalkanes to Bicyclo[2.1.0]pentanes

  摘要：

  Eight symmetrically disubstituted 3,5-diaryl-4,4-dimethylisopyrazoles 6 with para and meta substituents (OMe, Me, H, F, Cl, Br, CN, NO2) and two unsymmetrically para-substituted derivatives (OMe and NO2; Me and CO(2)Me) were synthesized from the corresponding 1,3-diaryl-2,2-dimethyl-1,3-propanediones 5, which in turn were readily available by 2,2-dimethylation of the diones 4. The acid-catalyzed cycloaddition of cyclopentadiene to the isopyrazoles 6, a Diels-Alder reaction with inverse electron demand, afforded the 1,4-diaryl-substituted gem-dimethyl azoalkanes 7 of the diazabicyco[2.2.1]hept-2-ene (DBH) type. The cycloadduct yields were strongly dependent on the nature of the aryl substituents and highest for the electron-withdrawing substituents. In acidic solution, the azoalkanes showed cycloreversion to generate an equilibrium between isopyrazole 6, cyclopentadiene, and azoalkane 7. For the p-methoxy derivative, cycloreversion was essentially quantitative, whereas only 20% cycloreversion occurred for the para nitro compound. A positive Hammett rho value (rho = 3.24 for 2 equiv of CF3COOH) was determined for the equilibrium constants of the acid-catalyzed [4(+) + 2] cycloaddition. The unsymmetrically substituted isopyrazoles gave two regioisomeric cycloadducts with a slight excess of one isomer. The direct and triplet-sensitized photochemical and thermal denitrogenation of the azoalkanes 7 gave in quantitative yields the 1,4-diaryl-substituted bicyclo[2.1.0]pentanes (BCP) 8 with retention of configuration. The azoalkanes 7 and the housanes 8 are more persistent than the related 1,4-diaryl-substituted DBH and BCP derivatives. The stabilizing effect is rationalized in terms of less favorable benzylic conjugation in the transition states for C-N (azoalkanes) and C-C (housanes) bond cleavage due to steric interactions between the geminal methyl groups at the methane bridge and the diaryl substituents at the bridgehead sites.

  DOI：

  10.1021/jo00093a010
• 作为产物：
  描述：

  2,2-二甲基-1,3-二苯基丙烷-1,3-二酮 在 一水合肼 、 三氟乙酸 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 反应 41.0h， 生成 (1α,4α,4aα,7aα)-4,4a,7,7a-Tetrahydro-8,8-dimethyl-1,4-diphenyl-1,4-methano-1H-cyclopenta[d]pyridazin
  参考文献：
  名称：

  由1,3-芳基环戊烷-1,3-二基三重基双基自由基的EPR D参数评估的3,5-二取代的枯基自由基中的电子间取代作用的可加性。

  摘要：

  3,3'，5,5'-四取代三重双自由基6（X = X'= H，NO（2），CH（3），OAc，OCH（3）的D参数（EPR零场分裂） ，NH（2）和OH）是在MTHF基质中于77 K下测定的，并通过其自旋密度依赖性，用作测定多取代苄基单基自由基中电子取代基效应的光谱工具。这些间二取代三元双自由基6与3,3'-二取代三元双自由基5的实验D值的线性相关性（m = 2.00 +/- 0.01，r（2）= 0.974）表明电子元的可加性在相应的3，5-二取代的枯基单自由基4中具有-取代基效应，并且通过理论（PM3-AUHF）自旋密度计算证实了后者。从而，

  DOI：

  10.1021/jo970756p

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。
• Stereochemical Memory in the Temperature-Dependent Photodenitrogenation of Bridgehead-Substituted DBH-Type Azoalkanes:  Inhibition of Inverted-Housane Formation in the Diazenyl Diradical through the Mass Effect (Inertia) and Steric Hindrance
  作者：Waldemar Adam、Hermenegildo García、Manfred Diedering、Vicente Martí、Massimo Olivucci、Emilio Palomares

  DOI：10.1021/ja026321n

  日期：2002.10.1

  syn/anti ratio of the housanes 2 depends on the extent and type of bridgehead substitution; the amount of the anti diastereomer (retention) follows the order Ph > Me > H, and double substitution is more effective than single. This stereochemical memory is interpreted in terms of the mass effect (inertia) of the substituents and steric interaction (size) between the substituents at the bridgehead and the methylene

  环戊烯退火 DBH 型偶氮烷烃 1 的光化学脱氮作用已在溶液中作为桥头取代和温度的函数进行了研究。对于所有衍生物，即未取代的 1a(H/H)、单甲基 1b(Me/H) 二甲基 1c(Me/Me)、单苯基 1d(Ph/H) 和二苯基 1e(Ph/Ph)，温度为syn 和 anti housanes 2 的依赖比例为直接光解中单线态（高温）和三线态（低温）反应通道之间的竞争提供了实验支持。housanes 2的syn/anti比例取决于桥头替换的程度和类型；反非对映体（保留）的量遵循Ph > Me > H的顺序，双取代比单取代更有效。这种立体化学记忆是根据取代基的质量效应（惯性）和桥头取代基与亚甲基桥之间的空间相互作用（大小）在瞬态二氮烯基双自由基构象 (1)DZ (exo- ax) 和 (1)DZ (exo-eq)。这些构象异构体是在 (1)(n,pi) 激发的偶氮烷烃衰变时冲动生成的，这是
• Beck, Karin; Huenig, Siegfried, Chemische Berichte, 1987, vol. 120, p. 477 - 484
  作者：Beck, Karin、Huenig, Siegfried

  DOI：——

  日期：——
• Radical Stabilization and Ground State Polar Substituent Effects in the Thermal Decomposition of Azoalkanes
  作者：Werner M. Nau、Heinrich M. Harrer、Waldemar Adam

  DOI：10.1021/ja00103a012

  日期：1994.11

  The thermolysis rates of a series of the 1,4-diaryl-2,3-diaza[2.2.1]bicyclohept-2 derivatives 1 with a large variety of aryl substituents (p-NH2, p-OMe, p-Me, H, p-F, p-Cl, p-Br, m-I, p-I, Nt-CN, p-CN, m-NO2, p-NOz, and p-CO(2)Me) have been determined to probe the electronic substituent effects in the thermal decomposition of azoalkanes. The correlation of the logarithmic relative rate constants versus the Creary substituent constants for radical stabilization (cf. Creary, X.; et al. J. Org. Chem. 1987, 52, 3254) improved considerably when polar effects (positive rho value) were included in the form of a two-parameter Hammett treatment. The importance of polar effects was also established in the reported thermolysis rate data for aryl-substituted azopropanes 2, azoethanes 3, azomethanes 4, azoneopentanes 5, and 3,5-diaryl-1-pyrazolines 6. The two-parameter analysis reveals that the thermal decomposition rates of azoalkanes are enhanced by radical- as well as anion-stabilizing substituents. On one hand, the ratio of the radical and polar reaction constants (rho(rad)+rho(pol)) serves as useful parameter to diagnose the radical nature in the decompositions of azoalkanes; thus, in general, radical effects dominate within the azoalkane 1-6 series. On the other hand, the overall sensitivity of the thermal decompositions toward substituent effects is reflected by the sum of the reaction constants (rho(rad)+rho(pol)) The polar effect is attributed to polar destabilization in the ground states of the azoalkanes, for which the polarized C-N bond is weakened by aryl substituents with electron accepters at the positively charged benzylic carbon atom. Semiempirical (AM1) calculations corroborate such polar effects for the azoalkanes 1-6 versus their corresponding diaryl-substituted alkanes 7-12.
• Electronic Substituent Effects on the Acid-Catalyzed [4+ + 2] Cycloaddition of Isopyrazoles with Cyclopentadiene and the Photochemical and Thermal Denitrogenation of the Resulting 1,4-Diaryl-7,7-dimethyl-2,3-diazabicyclo[2.2.1]hept-2-ene Azoalkanes to Bicyclo[2.1.0]pentanes
  作者：Waldemar Adam、Heinrich M. Harrer、Werner M. Nau、Karl Peters

  DOI：10.1021/jo00093a010

  日期：1994.7

  Eight symmetrically disubstituted 3,5-diaryl-4,4-dimethylisopyrazoles 6 with para and meta substituents (OMe, Me, H, F, Cl, Br, CN, NO2) and two unsymmetrically para-substituted derivatives (OMe and NO2; Me and CO(2)Me) were synthesized from the corresponding 1,3-diaryl-2,2-dimethyl-1,3-propanediones 5, which in turn were readily available by 2,2-dimethylation of the diones 4. The acid-catalyzed cycloaddition of cyclopentadiene to the isopyrazoles 6, a Diels-Alder reaction with inverse electron demand, afforded the 1,4-diaryl-substituted gem-dimethyl azoalkanes 7 of the diazabicyco[2.2.1]hept-2-ene (DBH) type. The cycloadduct yields were strongly dependent on the nature of the aryl substituents and highest for the electron-withdrawing substituents. In acidic solution, the azoalkanes showed cycloreversion to generate an equilibrium between isopyrazole 6, cyclopentadiene, and azoalkane 7. For the p-methoxy derivative, cycloreversion was essentially quantitative, whereas only 20% cycloreversion occurred for the para nitro compound. A positive Hammett rho value (rho = 3.24 for 2 equiv of CF3COOH) was determined for the equilibrium constants of the acid-catalyzed [4(+) + 2] cycloaddition. The unsymmetrically substituted isopyrazoles gave two regioisomeric cycloadducts with a slight excess of one isomer. The direct and triplet-sensitized photochemical and thermal denitrogenation of the azoalkanes 7 gave in quantitative yields the 1,4-diaryl-substituted bicyclo[2.1.0]pentanes (BCP) 8 with retention of configuration. The azoalkanes 7 and the housanes 8 are more persistent than the related 1,4-diaryl-substituted DBH and BCP derivatives. The stabilizing effect is rationalized in terms of less favorable benzylic conjugation in the transition states for C-N (azoalkanes) and C-C (housanes) bond cleavage due to steric interactions between the geminal methyl groups at the methane bridge and the diaryl substituents at the bridgehead sites.