4,4-dimethyl-3,5-diphenyl-4H-pyrazole | 30169-45-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 4,4-dimethyl-3,5-diphenyl-4H-pyrazole
• 英文别名: 4,4-dimethyl-3,5-diphenyl-4H-pyrazole；4,4-dimethyl-3,5-diphenylpyrazole
• CAS: 30169-45-0
• 化学式: C₁₇H₁₆N₂
• 分子量: 248.327
• InChiKey: LYRPGZWRXNELOP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 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：

  4,4-dimethyl-3,5-diphenyl-4H-pyrazole 在 氧气 作用下， 以 乙醚 、 丙酮 为溶剂， 反应 21.0h， 生成 3,4,4-trimethyl-4,5-dihydro-5-hydroperoxy-3,5-diphenyl-3H-pyrazoles
  参考文献：
  名称：

  Oxygen-atom transfer reagents: New, reactive α-azohydroperoxides

  摘要：

  DOI：

  10.1016/s0040-4039(00)96020-9
• 作为产物：
  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

文献信息

• Additivity of the Electronic <i>Meta</i>-Substituent Effect in 3,5-Disubstituted Cumyl Radicals Assessed by the EPR <i>D</i> Parameter of 1,3-Arylcyclopentane-1,3-diyl Triplet Diradicals
  作者：Waldemar Adam、Heinrich M. Harrer、Wiebke Maas

  DOI：10.1021/jo970756p

  日期：1997.10.1

  experimental D values of these meta-disubstituted triplet diradicals 6 versus the 3,3'-disubstituted triplet diradicals 5 demonstrates the additivity of the electronic meta-substituent effect in the corresponding 3,5-disubstituted cumyl monoradicals 4 and is corroborated by theoretical (PM3-AUHF) spin density calculations for the latter. Thus, the combined use of the experimental D parameter and semiempirically

  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，
• 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。
• SYNTHESIS OF trans-3-CHLORO-4,4,5-TRIMETHYL-3,5-DIPHENYL- 4.5-DIHYDRO-3H-PYRAZOLE
  作者：John Szwec、Pedro C. Vasquez、Paul J. Franklin、G. Davon Kennedy、A.L. Baumstark

  DOI：10.1515/hc.2004.10.2-3.133

  日期：2004.1

  tosyl chloride Results and Discussion The reaction of methyl lithium with 4,4-dimethyl-3,5-diphenyl-4/-/-pyrazole produced intermediate 1 which upon addition of an equivalent of p-toluenesulfonyl chloride produced compound 2 in excellent yield No evidence for N-tosylation was found. Compound 2 was identified initially by its unique H NMR characteristic spectrum in which one of the 4,4-dimethyl groups

  3,4,4-三甲基-3,4-二氢-3,5-二苯基-2H-吡唑的锂盐1与甲苯磺酰氯的反应出人意料地以高产率产生C-氯化吡唑啉2。简介 之前，我们开发了一种合成 5-乙酰氧基五取代的吡唑啉（4,5-二氢-3H-吡唑）的路线，作为合成高度取代的环丙烷的方法的一部分 具体而言，将甲基锂加成到环状吖嗪生成环状腙阴离子中间体。在早期的工作中，进行苯甲酰化以稳定这些对空气敏感的化合物。最近，需要将五取代的 3,4-二氢-2H-吡唑的 N-甲苯磺酰基衍生物作为中间体进行进一步研究。我们在这里报告了通过锂 3,4 的 C-氯化合成反式-3-氯-4,4,5-三甲基-3,5-二苯基-4,5-二氢-3H-吡唑。4 三甲基-3,4-二氢-3,5-二苯基-2H-吡唑与甲苯磺酰氯 结果与讨论 甲基锂与 4,4-二甲基-3,5-二苯基-4/-/-吡唑反应生成中间体 1在加入等量的对甲苯磺酰氯后，以极好的收率生成化合物 2
• SYNTHESIS OF 4,5-DIHYDRO-3,4,4,5,5-PENTASUBSTITUTED- N-TOSYL- 1H-PYRAZOLES
  作者：Phong Truong、G. Davon Kennedy、Pedro C. Vasquez、A.L. Baumstark

  DOI：10.1515/hc.2008.14.6.449

  日期：2008.1

  5-dihydro-N-tosyl1//-pyrazoles. Introduction Our interest in the synthesis of highly substituted pyrazolines as reagents for oxidation (cyclic azohydroperoxides) or as precursors to the synthesis of highly substituted cyclopropanes required the synthesis of 4,5-dihydro-3,4,4,5,5pentasubstituted-1//-pyrazoles and various derivatives. These substituted 4,5-dihydro1//-pyrazoles are generally extremely sensitive

  将甲基或苯基锂添加到 3,4,4,5-四取代-4//吡唑 (la-b) 中，顺利地产生了 4,5dihydro-3,4,4,5,5-pentalocated-1 的极其空气敏感的阴离子//-吡唑(2a-c)，其通过与甲苯磺酰氟反应以低到非常好的产率转化为N-甲苯磺酰化化合物3a-c。两步法是制备 4,5-二氢-N-甲苯磺酰基1//-吡唑的便捷一锅法。引言 我们对合成高度取代的吡唑啉作为氧化试剂（环状偶氮氢过氧化物）或作为合成高度取代的环丙烷的前体的兴趣需要合成 4,5-dihydro-3,4,4,5,5pentalocated-1/ /-吡唑和各种衍生物。这些取代的 4,5-二氢 1//-吡唑通常对空气氧化极其敏感并且通常难以处理。N-甲苯磺酸化衍生物需要作为合成六取代吡唑啉的前体。有趣的是，令人惊讶的是，关于 4,5-二氢-l //-吡唑的 N-甲苯磺酰化的文献很少。Engel 报道了 4
• SYNTHESIS OF 3,3,4,4,5-PENTASUBSTITUTED-5-VINYL-4,5-DIHYDRO-3H-PYRAZOLES: ROUTE TO VINYLCYCLOPROPANES
  作者：Kishia K. Towns、Pedro C. Vásquez、G. Davon Kennedy、A.L. Baumstark

  DOI：10.1515/hc.2006.12.5.337

  日期：2006.1

  5-dihydro-3H-pyrazoles, pyrazolines 2a-b, in fair yield. Thermal decomposition of 2a yielded the highly substituted vinylcyclopropane, 3, as the only observable product.. Previously, we have reported methodology for the synthesis of hexasubstituted 4,5-dihydro-3Hpyrazoles (pyrazolines) based on procedures developed for the synthesis of cyclic a-azohydroperoxides. The new route to highly substituted pyrazolines involved

  乙烯基取代的 3,4-二氢-2H-吡唑、la (R=Ph) 和 b (R=Me) [通过乙烯基锂与相应的环状吖嗪反应合成] 与碘苯二乙酸酯的反应产生乙烯基取代的-4,5-二氢-3H-吡唑，吡唑啉2a-b，产率一般。2a 的热分解产生了高度取代的乙烯基环丙烷 3，作为唯一可观察到的产物。 之前，我们已经报道了基于为合成环 a 开发的程序合成六取代 4,5-二氢-3H吡唑（吡唑啉）的方法-偶氮氢过氧化物。获得高度取代的吡唑啉的新途径包括两个基本步骤。最初的步骤是将甲基锂或苯基锂添加到环状吖嗪（4H-吡唑）中以产生 3,4-二氢-2H吡唑。这些反应性中间体与四乙酸铅在各种溶剂中的后续反应产生高产率的高度取代的乙酰氧基或含烷氧基的吡唑啉。高度取代的吡唑啉的热分解被证明是合成选定的六取代环丙烷的有用途径。对于机理研究，需要该系列中的乙烯基取代化合物。然而，文献中似乎没有关于向 4H-吡唑添加乙烯基锂