bis-(1-p-tolyl-ethylidene)-hydrazine

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: bis-(1-p-tolyl-ethylidene)-hydrazine
• 英文别名: 4'-Methylacetophenone azine；1,2-bis(1-(p-tolyl)ethylidene)hydrazine；Methyl-p-tolyl-ketazin；p-Methylacetophenonketazin；4-Methylacetophenonazin；Bis-(1-p-tolyl-aethyliden)-hydrazin；Bis-1-p-tolyl-ethyliden-diazin；p-Methyl-acetophenonazin；1-(4-methylphenyl)-N-[1-(4-methylphenyl)ethylideneamino]ethanimine
• 化学式: C₁₈H₂₀N₂
• 分子量: 264.37
• InChiKey: JVDVHQDNGONESM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 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：

  bis-(1-p-tolyl-ethylidene)-hydrazine 在 氯 作用下， 以 二氯甲烷 为溶剂， 生成 1.1'-Dichlor-1.1'-di-tolyl-(4)-1.1'-azoaethan
  参考文献：
  名称：

  The electrochemical reduction of 1,4-dichloroazoethanes: Reductive elimination of chloride to form aryl azines

  摘要：

  A series of 1,4-dichloroazoethanes (1-X/Y, X and Y = 4-NO2, 4-CN. 4-CH3 or 4-H) were studied in N,N-dimethylformamide using cyclic voltammetry. constant potential sweep voltammetry (CPSW) and constant potential electrolysis. The voltammograms of 1-X/Y exhibit an irreversible two-electron wave corresponding to dissociative electron transfer (DET) reduction of the carbon-chlorine bond resulting in formation of the azines 2-X/Y in quantitative yield. Additional redox waves correspond to the reversible reduction of the azines to the 2-X/Y center dot- radical anion and 2-X/Y2- dianion consecutively, with the exception of 1-NO2/NO2 where both NO2 groups are reduced simultaneously in a two-electron reversible wave. Thermodynamic and kinetic parameters were determined from CPSW: the standard reduction potentials (E degrees) vary between -0.7 and -1.3 V versus SCE as a function of electron-withdrawing substituent; the heterogeneous rate constants (k(het)) are consistent with a slow heterogeneous electron transfer with values ranging from 10(-3) to 10(-5) cm s(-1) : the transfer coefficients (alpha) for 1-NO2/NO2 and 1-NO2/H are greater than 0.5, indicative of a stepwise DET mechanism for the C-Cl bond cleavage while the remaining 1-X/Y compounds have alpha values between 0.35 and 0.5, and the intrinsic barriers are all significantly lower than predicted for a concerted DET. thereby also suggesting a stepwise DET mechanism. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.electacta.2010.04.080
• 作为产物：
  描述：

  1.1'-Dichlor-1.1'-di-tolyl-(4)-1.1'-azoaethan 在 四丁基高氯酸铵 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 bis-(1-p-tolyl-ethylidene)-hydrazine
  参考文献：
  名称：

  The electrochemical reduction of 1,4-dichloroazoethanes: Reductive elimination of chloride to form aryl azines

  摘要：

  A series of 1,4-dichloroazoethanes (1-X/Y, X and Y = 4-NO2, 4-CN. 4-CH3 or 4-H) were studied in N,N-dimethylformamide using cyclic voltammetry. constant potential sweep voltammetry (CPSW) and constant potential electrolysis. The voltammograms of 1-X/Y exhibit an irreversible two-electron wave corresponding to dissociative electron transfer (DET) reduction of the carbon-chlorine bond resulting in formation of the azines 2-X/Y in quantitative yield. Additional redox waves correspond to the reversible reduction of the azines to the 2-X/Y center dot- radical anion and 2-X/Y2- dianion consecutively, with the exception of 1-NO2/NO2 where both NO2 groups are reduced simultaneously in a two-electron reversible wave. Thermodynamic and kinetic parameters were determined from CPSW: the standard reduction potentials (E degrees) vary between -0.7 and -1.3 V versus SCE as a function of electron-withdrawing substituent; the heterogeneous rate constants (k(het)) are consistent with a slow heterogeneous electron transfer with values ranging from 10(-3) to 10(-5) cm s(-1) : the transfer coefficients (alpha) for 1-NO2/NO2 and 1-NO2/H are greater than 0.5, indicative of a stepwise DET mechanism for the C-Cl bond cleavage while the remaining 1-X/Y compounds have alpha values between 0.35 and 0.5, and the intrinsic barriers are all significantly lower than predicted for a concerted DET. thereby also suggesting a stepwise DET mechanism. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.electacta.2010.04.080

文献信息

• Rhodium ion catalyzed decomposition of aryldiazoalkanes
  作者：B.K.Ravi Shankar、Harold Shechter

  DOI：10.1016/s0040-4039(00)87320-7

  日期：1982.1

  Aryldiazomethanes are converted by rhodium(II) acetate and iodorhodium(III) tetraphenylporphyrin to cis- rather than trans-1,2-diarylethylenes. Secondary aryldiazoalkanes react with rhodirum(II) acetate to give azines.

  芳族重氮甲烷被乙酸铑（II）和异碘鎓（III）四苯基卟啉转化为顺式而不是反式1，2-二芳基乙烯。仲芳基重氮烷与乙酸Rhodirum（II）反应生成杂志。
• 一种高效合成吲哚和异喹啉衍生物的方法
  申请人：中国科学院兰州化学物理研究所

  公开号：CN105218426A

  公开（公告）日：2016-01-06

  本发明公开了一种取代吲哚和异喹啉的制备方法，属于有机化学合成技术领域。该方法采用以氧气为氧化剂，各种取代基取代的炔烃与芳胺或腙为起始原料，通过过渡金属催化，得到含吲哚或异喹啉结构的化合物。该反应原料、氧化剂及催化剂廉价易得，合成工艺简单，大大降低了合成成本；反应条件温和，产率高，易于工业化；反应原料及催化剂清洁无毒，对环境污染小。该类化合物及其衍生物作为重要的精细化学品，在医药、农药、香料和光电等行业获得广泛应用。
• Preparation of 5,5-Bis(ethoxycarbonyl)-5,6-dihydro-3,7-diaryl-4<i>H</i>-1,2-diazepines and Their Halogenations
  作者：Otohiko Tsuge、Kichinosuke Kamata、Seiichi Yogi

  DOI：10.1246/bcsj.50.2153

  日期：1977.8

  5,5-Bis(ethoxycarbonyl)-5,6-dihydro-3,7-diaryl-4H-1,2-diazepines (4) were prepared by the condensation of α-bromoacetophenone azines with diethyl malonate in the presence of sodium ethoxide. Halogenation of 4 afforded 7,7-bis(ethoxycarbonyl)-2,5-diaryl-3,4-diazanorcaradiene, 4,6-dihalodihydrodiazepines, 1-halodiazanorcaradienes, and/or 4,4,6,6-tetrachlorodihydrodiazepine, whose relative yields depended upon the reaction conditions. Dehalogenation of the halogenated products was also investigated.

  5,5-双(乙氧羰基)-5,6-二氢-3,7-二芳基-4H-1,2-二氮杂革（4）通过α-溴苯甲酮腈与二乙基丙二酸酯在乙醇钠存在下的缩合反应制备而成。将4进行卤化处理，得到了7,7-双(乙氧羰基)-2,5-二芳基-3,4-二氮杂诺环二烯、4,6-二卤二氢二氮杂革、1-卤二氮杂诺环二烯和/或4,4,6,6-四氯二氢二氮杂革，其相对产率取决于反应条件。此外，还研究了卤化产物的脱卤反应。
• Synthesis of Sulfones by Iron-Catalyzed Decomposition of Sulfonylhydrazones
  作者：José Barluenga、María Tomás-Gamasa、Fernando Aznar、Carlos Valdés

  DOI：10.1002/ejoc.201001492

  日期：2011.3

  The Fe-catalyzed decomposition of sulfonylhydrazones gives rise to sulfones. The reaction is quite general and allows the preparation of sulfones from a variety of aryl, alkyl, and α,β-unsaturated aldehydes and ketones. Crossover experiments reveal that the reaction is an intermolecular process, which may proceed by nucleophilic attack of the sulfinate anion on an iron carbene complex.

  磺酰腙的Fe催化分解产生砜。该反应非常普遍，允许从各种芳基、烷基和 α,β-不饱和醛和酮制备砜。交叉实验表明，该反应是一个分子间过程，可以通过亚磺酸根阴离子对铁卡宾配合物的亲核攻击来进行。
• Cp*Co(<scp>iii</scp>)-catalyzed annulation of azines by C–H/N–N bond activation for the synthesis of isoquinolines
  作者：Dewal S. Deshmukh、Prashant A. Yadav、Bhalchandra M. Bhanage

  DOI：10.1039/c9ob00174c

  日期：——

  and external oxidant free approach has been disclosed for the synthesis of isoquinolines. Azines were employed for annulation reactions with alkynes via sequential C–H/N–N bond activation using an air-stable cobalt catalyst. The method takes advantage of the incorporation of both the nitrogen atoms of azines into the desired isoquinoline products, offering the highest atom economy. In addition, the

  在此，已经公开了用于合成异喹啉的有效的，原子经济的和无外部氧化剂的方法。叠氮被用于通过空气稳定的钴催化剂通过连续的C–H / N–N键活化与炔烃进行环化反应。该方法利用了将两个氮原子都掺入所需的异喹啉产物中的优点，从而提供了最高的原子经济性。此外，开发的协议可在外部氧化剂以及无银盐的条件下工作。此外，已建立的方法具有相对较宽的底物范围，具有较高的产品产量和高达克级的可扩展性。