4,4'-dinitro-4''-methoxytriphenylamine

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4,4'-dinitro-4''-methoxytriphenylamine
• 英文别名: 4-methoxy-N,N-bis(4-nitrophenyl)aniline；N-(4-methoxyphenyl)-4-nitro-N-(4-nitrophenyl)aniline
• 化学式: C₁₉H₁₅N₃O₅
• 分子量: 365.345
• InChiKey: RBKLZBRQAJBYJU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  27
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4,4'-dinitro-4''-methoxytriphenylamine 在 palladium 10% on activated carbon 、 一水合肼 、 三乙胺 作用下， 以 乙醇 、 水 、 二甲基亚砜 为溶剂， 反应 82.0h， 生成 4,4'-bis[(4-nitrophenyl)amino]-4''-methoxytriphenylamine
  参考文献：
  名称：

  一种含七苯三胺-双荧光团结构的二胺单体及 制备和应用，聚酰胺、聚酰亚胺及制备和应用

  摘要：

  本发明提供了一种含七苯三胺‑双荧光团结构的二胺单体及制备和应用，聚酰胺、聚酰亚胺及制备和应用，属于电控荧光技术领域。以本发明所述含七苯三胺‑双荧光团结构的二胺单体为单体制备得到的聚酰胺或聚酰亚胺可以在保持聚合物热稳定性的同时，提高其溶解性和成膜性，并赋予聚合物优异的电控荧光性能。根据实施例的记载，本发明提供的由含七苯三胺‑双荧光团结构的二胺单体制备的聚酰胺或聚酰亚胺的电控荧光性能显著提高。

  公开号：

  CN111423333B
• 作为产物：
  描述：

  甲氧苯胺 、 对氟硝基苯 在 cesium fluoride 作用下， 以 二甲基亚砜 为溶剂， 生成 4,4'-dinitro-4''-methoxytriphenylamine
  参考文献：
  名称：

  新型的三苯胺基聚酰胺：在室温下通过苯并恶嗪-异氰化物化学方法的高效制备和电致变色性能研究

  摘要：

  通过霍夫曼对其伯胺前体进行处理，成功合成了一种新型的基于三苯胺（TPA）的二异氰酸酯衍生物-4-异氰基-N-（4-异氰基苯基）-N-（4-甲氧基苯基）苯胺（M1）（2）。在室温下，以M1和双官能苯并恶嗪为起始单体，通过有效的苯并恶嗪-异氰化物化学（BIC）成功地合成了一系列在主链中包含TPA单元的聚酰胺（P1-P3）。P1–P3的化学结构已通过FT-IR验证，11 H NMR和凝胶渗透色谱法（GPC）分析。通过溶液涂布（使用DMSO作为溶剂）制备聚合物薄膜，并通过循环伏安法（CV）研究P1-P3的电化学性能。P1-P3表现出单步高度可逆的氧化过程，反映出它们良好的电化学活性。聚合物的电致变色性质通过光谱电化学技术进一步分析。当施加的电压达到〜0.65 V时，P1-P3的UV-vis光谱在〜750 nm处出现新的吸收带，并伴随着明显的视觉颜色变化（从无色变为蓝绿色）。P1-P3的响应时间和显

  DOI：

  10.1016/j.dyepig.2020.108206

文献信息

• Study of Ultrasound Promoted Aromatic Nucleophilic Substitution of Halobenzenes with Amines
  作者：Mária Mečiarová、Štefan Toma、Jana Podlesná、Michal Kiripolský、Ivana Císařová

  DOI：10.1007/s00706-002-0505-8

  日期：2002.12.1

   The sonochemical nucleophilic aromatic substitution of substituted haloarenes with different amines were studied. The reaction course was found to be strongly depended on basicity, bulkiness, and boiling point of amines as well as on the electron-withdrawing property of the substituents.

   研究了用不同的胺对卤代芳烃进行声化学亲核取代。发现反应过程强烈地依赖于胺的碱性，膨松度和沸点以及取代基的吸电子性能。
• Highly stable anodic green electrochromic aromatic polyamides: synthesis and electrochromic properties
  作者：Cha-Wen Chang、Guey-Sheng Liou、Sheng-Huei Hsiao

  DOI：10.1039/b613140a

  日期：——

  A 4-methoxy-substituted triphenylamine containing the aromatic diamine, 4,4′-diamino-4″-methoxytriphenylamine (2), was synthesized by the caesium fluoride-mediated condensation of p-anisidine with 4-fluoronitrobenzene, followed by palladium-catalyzed hydrazine reduction of the dinitro intermediate. A series of new polyamides with pendent 4-methoxy-substituted triphenylamine (TPA) units having inherent viscosities of 0.27–1.39 dL g−1 were prepared via the direct phosphorylation polycondensation of various dicarboxylic acids and the diamine (2). All the polymers were readily soluble in many organic solvents, such as N-methyl-2-pyrrolidinone (NMP) and N,N-dimethylacetamide (DMAc), and could be solution-cast into tough and flexible polymer films. These aromatic polyamides had useful levels of thermal stability associated with their relatively high softening temperature (242–282 °C), 10% weight-loss temperatures in excess of 470 °C, and char yields at 800 °C in nitrogen higher than 60%. The hole-transporting and electrochromic properties are examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the polyamide films cast onto an indium-tin oxide (ITO)-coated glass substrate exhibited reversible oxidation at 0.73–0.79 V versus Ag/AgCl in acetonitrile solution, and revealed excellent stability of electrochromic characteristics with a color change from colorless to green at applied potentials ranging from 0.00 to 1.05 V. These anodically polymeric electrochromic materials not only showed excellent reversible electrochromic stability with good green coloration efficiency (CE = 374 cm2 C−1) but also exhibited high contrast of optical transmittance change (ΔT %) up to 85% at 787 nm and 30% at 391 nm. After over 1000 cyclic switches, the polymer films still exhibited excellent stability of electrochromic characteristics.

  合成了一种含有芳香族二胺的4-甲氧基取代三苯胺，4,4′-二氨基-4″-甲氧基三苯胺（2），其合成方法为用氟化铯促进对氨基苯甲醚与4-氟硝基苯的缩合反应，随后通过钯催化的肼还原二硝基中间体。通过不同二羧酸与二胺（2）的直接磷酸化缩聚反应，制备了一系列新型聚酰胺，这些聚酰胺具有悬挂的4-甲氧基取代三苯胺（TPA）单元，固有粘度为0.27–1.39 dL g−1。所有聚合物在多种有机溶剂中易于溶解，如N-甲基-2-吡咯烷酮（NMP）和N,N-二甲基乙酰胺（DMAc），并可溶液铸造成坚韧且柔韧的聚合物薄膜。这些芳香族聚酰胺具有实用的热稳定性，其软化温度较高（242–282 °C），10%失重温度超过470 °C，并且在800 °C时在氮气中产炭率超过60%。通过电化学和光谱电化学方法研究了其载流子传输和电致变色特性。铸在铟锡氧化物（ITO）涂层玻璃基材上的聚酰胺薄膜的循环伏安图在0.73–0.79 V（相对于Ag/AgCl）时显示出可逆氧化，且在施加电压范围从0.00到1.05 V时，电致变色特性表现出优异的稳定性，颜色从无色变为绿色。这些阳极聚合电致变色材料不仅表现出优良的可逆电致变色稳定性和良好的绿色着色效率（CE = 374 cm² C−1），而且在787 nm时光学透过率变化的对比度高达85%，在391 nm时达到30%。经过超过1000次循环切换，聚合物薄膜仍表现出优异的电致变色特性稳定性。
• Novel anodic electrochromic aromatic polyamides with multi-stage oxidative coloring based on N,N,N′,N′-tetraphenyl-p-phenylenediamine derivatives
  作者：Cha-Wen Chang、Guey-Sheng Liou

  DOI：10.1039/b810750e

  日期：——

  A series of novel aromatic polyamides with pendent 4,4′-dimethoxy-substituted triphenylamine (TPA) units were prepared via the direct phosphorylation polycondensation from a new dicarboxylic acid monomer, N,N-bis(4-carboxyphenyl)-N′,N′-di(4-methoxyphenyl)-1,4-phenylenediamine (4), and various aromatic diamines. These polyamides were amorphous with good solubility in many organic solvents, such as N-methyl-2-pyrrolidinone (NMP) and N,N-dimethylacetamide (DMAc), and could be solution-cast into flexible polymer films. They had excellent levels of thermal stability associated with their relatively high glass-transition temperatures (233–308 °C). These polymers exhibited strong UV-vis absorption bands at 351–363 nm in NMP solution. Their photoluminescence spectra showed maximum bands around 450–504 nm. The hole-transporting and electrochromic properties are examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the polyamide 6g prepared from the dicarboxylic acid monomer (4) with a structurally similar diamine monomer N,N-bis(4-aminophenyl)-N′,N′-di(4-methoxyphenyl)-1,4-phenylenediamine (5g) exhibited four reversible oxidation redox couples in acetonitrile solution at Eonset = 0.35, E1/2 = 0.64, 0.84, and 0.99 V, respectively. After over 3000 cyclic switches for green color, the films of polyamide 6g still showed excellent continuous cyclic stability of electrochromism.

  一种新型二羧酸单体--N,N-双（4-羧基苯基）-Nâ²,Nâ²-二（4-甲氧基苯基）-1,4-苯二胺（4）和多种芳香族二胺通过直接磷酸化缩聚反应制备了一系列具有下垂的 4,4â²-二甲氧基取代三苯胺（TPA）单元的新型芳香族聚酰胺。这些聚酰胺是无定形的，在 N-甲基-2-吡咯烷酮（NMP）和 N,N-二甲基乙酰胺（DMAc）等多种有机溶剂中具有良好的溶解性，可以溶液浇铸成柔性聚合物薄膜。这些聚合物具有极佳的热稳定性，其玻璃化转变温度相对较高（233â308 °C）。在 NMP 溶液中，这些聚合物在 351- 363 nm 处显示出强烈的紫外-可见吸收带。它们的光致发光光谱在 450-504 nm 处显示出最大波段。电化学和光谱电化学方法检测了空穴传输和电致变色特性。由二羧酸单体（4）与结构相似的二胺单体 N,N-双（4-氨基苯基）-Nâ²,Nâ²-二（4-甲氧基苯基）-1,4-苯二胺（5g）制备的聚酰胺 6g 的循环伏安图显示，在乙腈溶液中，Eonset = 0.35、E1/2 = 0.64、0.84 和 0.99 V 时，存在四个可逆氧化还原偶。经过 3000 多次绿色循环切换后，聚酰胺 6g 薄膜的电致色性仍表现出极佳的连续循环稳定性。
• Pd-PEPPSI-IPent^Cl: An Effective Catalyst for the Preparation of Triarylamines
  作者：Ka Hou Hoi、Jennifer A. Coggan、Michael G. Organ

  DOI：10.1002/chem.201203379

  日期：2013.1.14

  Third times a charm: A new Pd–NHC catalyst, Pd‐PEPPSI‐IPentCl, has been developed for applications in amination reactions for the preparation of triarylamines. The catalyst can be used under mild conditions (carbonate base/dioxane, 80 °C) to perform multiple aminations in sequence from simple aniline derivatives that contain highly base‐sensitive functional groups.

  第三次魅力：开发了一种新的Pd-NHC催化剂Pd-PEPPSI-IPent Cl，用于制备三芳基胺的胺化反应中。该催化剂可在温和条件下（碳酸盐碱/二恶烷，80°C）使用，以从含有高度碱敏感官能团的简单苯胺衍生物开始依次进行多种胺化反应。
• Novel triphenylamine-based polyamides: Efficient preparation via benzoxazine-isocyanide-chemistry at room temperature and electrochromic properties investigation
  作者：Chang Yang、Wei Shi、Xin Chen、Kesong Zhang、Xinyu Zhou、Xu Sun、Sheng Ding、Sai Liu、Zhengfeng Xie

  DOI：10.1016/j.dyepig.2020.108206

  日期：2020.5

  solution coating (using DMSO as solvent), and electrochemical properties of P1–P3 were investigated by cyclic voltammetry (CV). P1–P3 exhibited single-step highly reversible oxidation process, reflecting their good electrochemical activity. Electrochromic properties of polymers were further analyzed by spectroelectrochemical techniques. New absorption bands at ∼750 nm appeared in UV–vis spectra of P1–P3

  通过霍夫曼对其伯胺前体进行处理，成功合成了一种新型的基于三苯胺（TPA）的二异氰酸酯衍生物-4-异氰基-N-（4-异氰基苯基）-N-（4-甲氧基苯基）苯胺（M1）（2）。在室温下，以M1和双官能苯并恶嗪为起始单体，通过有效的苯并恶嗪-异氰化物化学（BIC）成功地合成了一系列在主链中包含TPA单元的聚酰胺（P1-P3）。P1–P3的化学结构已通过FT-IR验证，11 H NMR和凝胶渗透色谱法（GPC）分析。通过溶液涂布（使用DMSO作为溶剂）制备聚合物薄膜，并通过循环伏安法（CV）研究P1-P3的电化学性能。P1-P3表现出单步高度可逆的氧化过程，反映出它们良好的电化学活性。聚合物的电致变色性质通过光谱电化学技术进一步分析。当施加的电压达到〜0.65 V时，P1-P3的UV-vis光谱在〜750 nm处出现新的吸收带，并伴随着明显的视觉颜色变化（从无色变为蓝绿色）。P1-P3的响应时间和显