N-(4-nitrophenyl)-N'-phenyl-1,4-phenylenediamine | 36629-08-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-(4-nitrophenyl)-N'-phenyl-1,4-phenylenediamine
• 英文别名: N-(4-nitrophenyl)-N'-phenyl-benzene-1,4-diamine；N-(4-nitro-phenyl)-N'-phenyl-p-phenylenediamine；N-(4-Nitro-phenyl)-N'-phenyl-p-phenylendiamin；1,4-Benzenediamine, N-(4-nitrophenyl)-N'-phenyl-；4-N-(4-nitrophenyl)-1-N-phenylbenzene-1,4-diamine
• CAS: 36629-08-0
• 化学式: C₁₈H₁₅N₃O₂
• 分子量: 305.336
• InChiKey: OOQLVBJPIMMTNZ-UHFFFAOYSA-N

物化性质

• 熔点：
  140 °C
• 沸点：
  527.5±30.0 °C(Predicted)
• 密度：
  1.308±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  69.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-(4-nitrophenyl)-N'-phenyl-1,4-phenylenediamine 在 palladium 10% on activated carbon 、 一水合肼 、 cesium fluoride 作用下， 以 乙醇 、 N,N-二甲基乙酰胺 、 二甲基亚砜 为溶剂， 反应 74.0h， 生成
  参考文献：
  名称：

  带有仲胺的新型基于三芳基胺的芳族聚酰胺：吡啶诱导的合成和氧化还原电势反转特性†

  摘要：

  制备了具有仲胺部分的新颖的基于三芳基胺的芳族聚酰胺，并将其用作吡啶的电化学检测器。为了证明仲胺与吡啶的离子氢键相互作用，研究了它们在不同吡啶上的电化学行为，从而导致明显的电势反转，这也得到原位吸收测量的支持。

  DOI：

  10.1039/c6tc03409h
• 作为产物：
  描述：

  对氟硝基苯 、 对氨基二苯胺 在 三乙胺 作用下， 以 二甲基亚砜 为溶剂， 反应 72.0h， 以78%的产率得到N-(4-nitrophenyl)-N'-phenyl-1,4-phenylenediamine
  参考文献：
  名称：

  带有仲胺的新型基于三芳基胺的芳族聚酰胺：吡啶诱导的合成和氧化还原电势反转特性†

  摘要：

  制备了具有仲胺部分的新颖的基于三芳基胺的芳族聚酰胺，并将其用作吡啶的电化学检测器。为了证明仲胺与吡啶的离子氢键相互作用，研究了它们在不同吡啶上的电化学行为，从而导致明显的电势反转，这也得到原位吸收测量的支持。

  DOI：

  10.1039/c6tc03409h

文献信息

• Synthesis and spectroscopic properties of aniline tetramers. Comparative studies
  作者：Irena Kulszewicz-Bajer、Izabela Różalska、Małgorzata Kuryłek

  DOI：10.1039/b311096f

  日期：——

  A new synthetic method involving SNAr coupling of 4-fluoronitrobenzene to arylamines, followed by the reduction of the nitro groups, has been developed. Two types of aniline oligomers, namely Ph/NH2 and NH2/NH2 tetramers have been prepared by this method. Tetramers in the leucoemeraldine and in the emeraldine oxidation states were characterized by NMR, UV-Vis-NIR, IR and mass spectroscopies. It shown that the NH2/NH2 tetramer oxidized to the emeraldine state forms two isomers: syn and anti. The oxidation of the Ph/NH2 tetramer leads to the creation of positional isomers, depending on the synthetic method.

  我们开发出了一种新的合成方法，即先将 4-氟硝基苯与芳基胺进行 SNAr 偶联，然后再还原硝基。通过这种方法制备了两种类型的苯胺低聚物，即 Ph/NH2 和 NH2/NH2 四聚物。通过核磁共振、紫外-可见-近红外光谱、红外光谱和质谱分析，对处于白绿宝石氧化态和绿宝石氧化态的四聚体进行了表征。结果表明，氧化成绿宝石态的 NH2/NH2 四聚体会形成两种异构体：同步异构体和反同步异构体。Ph/NH2 四聚体的氧化会产生位置异构体，具体取决于合成方法。
• On the Formation of Mauvein: Mechanistic Considerations and Preparative Results
  作者：Christoph Heichert、Horst Hartmann

  DOI：10.1515/znb-2009-0622

  日期：2009.6.1

  The reaction of aniline (AH₂) with an oxidizing agent in acidic solution gives rise to the formation of a mixture of products containing, besides a variety of oligoanilines named as Aniline Black or Polyaniline, Mauvein as a deeply purple phenazine derivative. Although this Mauvein synthesis was developed by W.H. Perkin more than 150 years ago and has opened the era of industrial dyestuff chemistry, the detailed mechanism of this reaction has remained rather unclear until today. The elucidation of the mechanism of the Mauvein formation as an oxidative coupling process of AH₂ is hindered by the fact that several different types of coupling reactions occur simultaneously. Among them the C,N-coupling reaction is the most important one and responsible for the formation of Polyaniline and Mauvein. It gives rise to the formation of, e. g. 2 different aniline dimers, 7 trimers and more than 20 tetramers including Mauvein as one representative of these tetramers. In the present study, the oxidative coupling of a mixture of AH₂ and 4-amino-4`-(N-anilino)-diphenylamine (TaH2) as one of the aniline trimers was studied in more detail. The reaction leads to the formation of Mauvein in satisfactory yields and, after some manipulations, widely free of byproducts. By using simple aniline derivatives as co-reagents in the oxidative coupling with TaH₂, the reaction can be extended to the synthesis of different Mauvein derivatives most of which have been unknown to date.

  苯胺（AH2）与氧化剂在酸性溶液中反应，形成一系列寡聚苯胺的混合物，其中包括被称为苯胺黑或聚苯胺的各种寡聚苯胺，以及一种深紫色的苯并咪唑衍生物——紫红色素。虽然这种紫红色素的合成方法是由W.H. Perkin在150多年前开发的，开创了工业染料化学的时代，但是直到今天，这种反应的详细机理仍然不太清楚。苯并咪唑的形成机理是AH2的氧化偶联过程，但由于同时发生几种不同类型的偶联反应，因此阐明其机理受到阻碍。其中，C，N偶联反应是最重要的反应之一，负责聚合形成聚苯胺和苯并咪唑。它导致形成2种不同的苯胺二聚体、7种三聚体和20多种四聚体，其中包括苯并咪唑作为这些四聚体的代表之一。在本研究中，对AH2和4-氨基-4'-(N-苯胺基)-二苯胺（TaH2）的混合物进行了更详细的氧化偶联研究。该反应以令人满意的产率形成苯并咪唑，并且在一些操作后，几乎没有副产物。通过使用简单的苯胺衍生物作为共反应剂与TaH2进行氧化偶联，可以将反应扩展到合成不同的苯并咪唑衍生物，其中大多数迄今尚未知晓。
• Lantz; Obellianne, Bulletin de la Societe Chimique de France, 1956, p. 311,315
  作者：Lantz、Obellianne

  DOI：——

  日期：——
• Synthesis and spectroscopic properties of linear oligoanilines
  作者：I. Rozalska、M. Kurylek、M. Franaszek、I. Kulszewicz-Bajer

  DOI：10.1080/15421400490482952

  日期：2004.1

  Two types of linear oligomers, namely Ph/NH2 and NH(2)lNH(2) end-capped oligoanilines have been synthesized by SNAr coupling/reduction sequence. The H-1 NMR spectra of obtained compounds are strongly influenced by electron withdrawing or electron donating effects of the terminal groups (NO2 or NH2, respectively). The UV-Vis spectra of nitroamines exhibit two peaks characteristic for two types of the phenylene substituents (-NH- or NO2), whereas UV-Vis spectra of oligoanilines show only one peak attributed to the Pi-Pi* transition in the phenylene rings. The oxidation of oligoanilines was also followed by UV-Vis spectroscopy.
• Novel triarylamine-based aromatic polyamides bearing secondary amines: synthesis and redox potential inversion characteristics induced by pyridines
  作者：Hung-Ju Yen、Jhe-Huang Lin、Yuhlong Oliver Su、Guey-Sheng Liou

  DOI：10.1039/c6tc03409h

  日期：——

  Novel triarylamine-based aramids with secondary amine moieties are prepared and utilized as electrochemical detectors for pyridines. Their electrochemical behavior with different pyridines was investigated in order to demonstrate the ionic hydrogen bonding interaction of the secondary amine with the pyridines, resulting in obvious potential inversion which is also supported by in situ absorption measurements

  制备了具有仲胺部分的新颖的基于三芳基胺的芳族聚酰胺，并将其用作吡啶的电化学检测器。为了证明仲胺与吡啶的离子氢键相互作用，研究了它们在不同吡啶上的电化学行为，从而导致明显的电势反转，这也得到原位吸收测量的支持。