N-(4-aminophenyl)-N'-phenyl-1,4-phenylenediamine | 36629-09-1

• 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-aminophenyl)-N'-phenyl-1,4-phenylenediamine
• 英文别名: 4-N-(4-anilinophenyl)benzene-1,4-diamine
• CAS: 36629-09-1
• 化学式: C₁₈H₁₇N₃
• 分子量: 275.353
• InChiKey: IMNFXMLWQIPLHA-UHFFFAOYSA-N

物化性质

• 熔点：
  154 °C(Solv: ligroine (8032-32-4))
• 沸点：
  504.5±25.0 °C(Predicted)
• 密度：
  1.230±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  21
• 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：
  50.1
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-(4-aminophenyl)-N'-phenyl-1,4-phenylenediamine 在 palladium diacetate 双(2-二苯基磷苯基)醚 、 silver(l) oxide 、 sodium t-butanolate 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 84.0h， 生成 N1-phenyl-N4-(4-(((4E,7E)-7-(phenylimino)benzo[c][1,2,5]thiadiazol-4(7H)-ylidene)amino)phenyl)benzene-1,4-diamine
  参考文献：
  名称：

  Synthesis and Characterization of p-Phenylenediamine Derivatives Bearing an Electron-Acceptor Unit

  摘要：

  Two series of aniline oligomers bearing fused heterocycles as an electron-acceptor unit were synthesized. They consist of aniline or its derivatives as an electron donor and benzothiadiazole (BT) or quinoxaline (QX) as an electron-acceptor unit. Benzothiadiazoles 1-3 were synthesized by palladium-catalyzed amination. Quinoxalines 4-6 were prepared by palladium-catalyzed amination or transformation from the benzothiadiazoles. These compounds showed a HOMO-LUMO gap smaller than those of their analogues such as thiophene-substituted BT/QXs. Cyclic voltammetry revealed that the electrochemical behavior is dependent on the position of the acceptor heterocycle. Chemical oxidation with Ag2O afforded the corresponding 1,4-quinonediimine derivatives as an E,E-isomer, stereoselectively. As for the BT pentamer analogues 2 and 3, the first oxidation selectively occurred at the amino group adjacent to the benzothiadiazole unit, giving the regiospecific half-oxidized derivatives. Furthermore, the fully oxidized derivative 24 was isolated and characterized.

  DOI：

  10.1021/jo048324j
• 作为产物：
  描述：

  对氨基二苯胺 在 盐酸 、 tin 、 三乙胺 作用下， 以 二甲基亚砜 为溶剂， 反应 123.0h， 生成 N-(4-aminophenyl)-N'-phenyl-1,4-phenylenediamine
  参考文献：
  名称：

  Synthesis and spectroscopic properties of aniline tetramers. Comparative studies

  摘要：

  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。

  DOI：

  10.1039/b311096f

文献信息

• One-pot propagation of (Hetero)Arylamines: Modular synthesis of diverse Amino-di(hetero)arylamines
  作者：Xueting Liang、Liang Xu、Cuihua Li、Xin Jia、Yu Wei

  DOI：10.1016/j.tet.2018.12.035

  日期：2019.2

  Formal propagation of (hetero)arylamine is achieved via a one-pot Buchwald–Hartwig C–N cross-coupling and nitro reduction sequence, enabling a rapid modular synthesis of diverse amino-di(hetero)arylamines from (hetero)arylamines and halogenated nitrobenzenes. Various functionalized aromatic amines with different electronic and steric environments can be efficiently prolongated to formally incorporate

  （杂）芳基胺的形式扩散是通过一锅Buchwald-Hartwig C-N交叉偶联和硝基还原序列实现的，从而可以从（杂）芳基胺和卤代硝基苯快速模块化合成各种氨基-二（杂）芳基胺。 。可以有效地延长具有不同电子和空间环境的各种官能化芳族胺，以正式引入另一种芳基氨基片段。该方法已成功地用于合成四十多种氨基二（杂）芳基胺。在寡聚苯胺和酪氨酸激酶抑制剂伊马替尼的合成中也证明了该方法的适用性。
• EPR and pulsed ENDOR study of intermediates from reactions of aromatic azides with group 13 metal trichlorides
  作者：Giorgio Bencivenni、Riccardo Cesari、Daniele Nanni、Hassane El Mkami、John C Walton

  DOI：10.3762/bjoc.6.84

  日期：——

  reactions of group 13 metal trichlorides with aromatic azides were examined by CW EPR and pulsed ENDOR spectroscopies. Complex EPR spectra were obtained from reactions of aluminium, gallium and indium trichlorides with phenyl azides containing a variety of substituents. Analysis of the spectra showed that 4-methoxy-, 3-methoxy- and 2-methoxyphenyl azides all gave 'dimer' radical cations [ArNHC(6)H(4)NH(2)](+*)

  通过 CW EPR 和脉冲 ENDOR 光谱检查第 13 族金属三氯化物与芳族叠氮化物的反应。从铝、镓和铟的三氯化物与含有多种取代基的苯基叠氮化物的反应中获得复杂的 EPR 光谱。光谱分析表明，4-甲氧基-、3-甲氧基-和 2-甲氧基苯基叠氮化物均产生“二聚体”自由基阳离子 [ArNHC(6)H(4)NH(2)](+*) 和三聚体 [ArNHC( 6)H(4)NHC(6)H(4)NH(2)](+*)，然后是聚合物。4-叠氮苯腈及其吸电子取代基不反应。一般来说，芳香族叠氮化物似乎与 AlCl(3) 反应最迅速，但这种试剂往往会产生很多聚合物。InCl(3) 是反应性最小的基团 13 卤化物。自由基阳离子的 DFT 计算提供了确凿的证据，并表明未配对的电子被容纳在广泛的 pi 离域轨道中。提出了一种机制来解释芳香叠氮化物还原转化为相应的苯胺，然后再转化为二聚体和三聚体。
• 화합물, 이를 포함하는 코팅 조성물, 이를 이용한 유기 발광 소자 및 이의 제조방법
  申请人：LG CHEM, LTD. 주식회사 엘지화학(120010134563) Corp. No ▼ 110111-2207995BRN ▼107-81-98139

  公开号：KR20190005591A

  公开（公告）日：2019-01-16

  본 명세서는 화학식 1의 화합물 및 이를 포함하는 코팅 조성물, 이를 이용한 유기 발광 소자 및 이의 제조 방법에 관한 것이다.

  这是关于化学式1的化合物及其包含的涂层组合物，以及利用它制造有机发光器件的规范书和制造方法。
• 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。
• Sandwich Dimer Complexes of Zinc Porphyrins Bearing Three-Dimensionally Oriented Redox-Active π-Conjugated Pendant Groups
  作者：Toshikazu Hirao、Kaori Saito

  DOI：10.1055/s-2002-20454

  日期：——

  Treatment of the zinc porphyrins bearing four dimensionally oriented phenylenediamine strands with a bidentate ligand, DABCO, led to the formation of the sandwich dimer complexes, in which the porphyrin moieties are surrounded by π-conjugated pendant groups.

  用双齿配体 DABCO 处理带有四维定向苯二胺链的锌卟啉，导致形成夹心二聚体复合物，其中卟啉部分被 π 共轭侧基包围。