4-chloro-4',4"-dimethyltriphenylamine | 58047-41-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-chloro-4',4"-dimethyltriphenylamine
• 英文别名: N-(p-Chlorphenyl)di-p-tolylamin；4-chloro-N,N-bis(4-methylphenyl)aniline；N-(4-chlorophenyl)-4-methyl-N-(4-methylphenyl)aniline
• CAS: 58047-41-9
• 化学式: C₂₀H₁₈ClN
• 分子量: 307.823
• InChiKey: FQIGPNNKZOMUEZ-UHFFFAOYSA-N

物化性质

• 沸点：
  444.4±45.0 °C(Predicted)
• 密度：
  1.161±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-chloro-4',4"-dimethyltriphenylamine 、 1-(吡啶-2-基)-1H-吲哚 在 1,1'-双(二苯基膦)二茂铁 、 nickel diacetate 、 lithium hexamethyldisilazane 作用下， 以 neat (no solvent) 为溶剂， 反应 16.0h， 以86%的产率得到4-methyl-N-(4-(1-(pyridin-2-yl)-1H-indol-2-yl)phenyl)-N-(p-tolyl)aniline
  参考文献：
  名称：

  在纯净条件下，吲哚与芳基氯化物的镍催化C（2）-H芳基化反应。

  摘要：

  在纯净条件下可实现吲哚和吡咯与芳基氯化物的镍催化区域选择性C（2）-H芳基化反应。该方法允许在80°C下使用用户友好且价格便宜的Ni（OAc）2 / dppf催化剂系统有效地偶联各种芳基氯化物。在反应条件下，可以很好地耐受多种官能团，例如卤化物，烷基醚，氟代烷基醚和硫醚，以及取代的胺，包括杂芳烃，如苯并噻唑基，吡咯基，吲哚基和咔唑基。初步的机理研究突出了芳基化反应的单电子转移（SET）途径。

  DOI：

  10.1021/acs.joc.9b01375
• 作为产物：
  描述：

  对溴甲苯 、 对氯苯胺 在 bis-triphenylphosphine-palladium(II) chloride 、 三苯基膦 、 sodium t-butanolate 作用下， 以 邻二甲苯 为溶剂， 反应 12.0h， 以90%的产率得到4-chloro-4',4"-dimethyltriphenylamine
  参考文献：
  名称：

  Effects of solvent and base on the palladium-catalyzed amination: PdCl2(Ph3P)2/Ph3P-catalyzed selective arylation of primary anilines with aryl bromides

  摘要：

  A readily accessible catalytic system, PdCl2(Ph3P)(2)/Ph3P, was developed for the selective arylation of primary anilines with aryl bromides. The strong influence of solvents and bases on the catalytic activity was observed. In refluxing o-xylene, triphenylphosphine shows high efficiency for Pd-catalyzed intermolecular amination reactions. By changing the bases, mono- and diarylation of primary amines could be selectively achieved in high yields. Moreover, the catalytic system showed good toleration for the steric hindrance of anilines. A series of N,N,N',N'-tetraaryl-1,1'-biphenyl-4,4'-diamines, important intermediates of OLED hole transport materials, were synthesized facilely via coupling reactions between 4,4'-diaminobiphenyls and aryl bromides. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.05.048

文献信息

• N-alkylation andN-arylation of anilines starting from a mild N?Mg reagent: Its activation causing the ?N?C? coupling to extend the unified structure-reactivity relationship
  作者：Koji Matsuo、Yoshiaki Shichida、Hiroshi Nishida、Satsuki Nakata、Masao Okubo

  DOI：10.1002/poc.610070103

  日期：1994.1

  New N-alkylation and N-arylation procedures starting from anilinomagnesium (ArNHMgBr) are reported. For N-alkylation with alkyl bromides, addition of hexamethylphosphoramide to an ArNHMgBr solution in tetrahydrofuran (THF) is effective. After heating at 55°C, N-monoalkylation product was obtained in 60–90% yield, slight dialkylation taking place. The combined use of aryliminodimagnesium [ArN(MgBr)2]

  据报道，从苯胺镁（ArNHMgBr）开始新的N-烷基化和N-芳基化程序。为了用烷基溴进行N-烷基化，向在四氢呋喃（THF）中的ArNHMgBr溶液中添加六甲基磷酰胺是有效的。在55°C加热后，以60-90％的收率获得N-单烷基化产物，发生少量的二烷基化反应。芳基二镁[ArN（MgBr）2 ]与α，ω-二溴代烷烃的组合使用可产生N-芳基氮杂环烷烃。对于N用碘代苯进行芳基化，用吡啶代替THF以及另外使用碘化亚铜（I）都是有效的。用碘代苯在115°C加热后，获得一元和二芳基化产物，其中前者占主导地位。ArNHMgBr和N，N，N '，N'-四甲基乙二胺作为铜物种的配体的组合使用可有效消除二芳基化和其他不希望的产物，并以极好的收率得到二芳基胺。该方法优于常规的Ullmann和Chapman方法。极性溶剂和铜盐是有效的添加剂，可将ArNHMgBr或ArN（MgBr）2与烷基和芳基卤化物“惰性结合”成
• Spirobifluorene derivative-based materials for electronic devices
  申请人：Merck Patent GmbH

  公开号：US10032989B2

  公开（公告）日：2018-07-24

  The present application relates to spirobifluorene derivatives of a formula (I), to the use thereof in electronic devices, and to processes for preparing said derivatives.

  本申请涉及式 (I) 的螺二芴衍生物、其在电子设备中的用途以及制备上述衍生物的工艺。
• SPIROBIFLUORENE DERIVATIVE-BASED MATERIALS FOR ELECTRONIC DEVICES
  申请人：Merck Patent GmbH

  公开号：US20180026188A1

  公开（公告）日：2018-01-25

  The present application relates to spirobifluorene derivatives of a formula (I), to the use thereof in electronic devices, and to processes for preparing said derivatives.
• [DE] MATERIALIEN AUF BASIS VON SPIROBIFLUORENDERIVATEN FÜR ELEKTRONISCHE VORRICHTUNGEN<br/>[EN] SPIROBIFLUORENE DERIVATIVE-BASED MATERIALS FOR ELECTRONIC DEVICES<br/>[FR] MATÉRIAUX À BASE DE DÉRIVÉS DE SPIROBIFLUORÈNE POUR DISPOSITIFS ÉLECTRONIQUES
  申请人：MERCK PATENT GMBH

  公开号：WO2016131521A1

  公开（公告）日：2016-08-25

  Die vorliegende Anmeldung betrifft Spirobifluoren-Derivate einer Formel (I), ihre Verwendung in elektronischen Vorrichtungen, sowie Verfahren zur Herstellung der genannten Derivate.
• Effects of solvent and base on the palladium-catalyzed amination: PdCl2(Ph3P)2/Ph3P-catalyzed selective arylation of primary anilines with aryl bromides
  作者：Liangzhen Cai、Xuanying Qian、Wenjing Song、Taoping Liu、Xiaochun Tao、Wanfang Li、Xiaomin Xie

  DOI：10.1016/j.tet.2014.05.048

  日期：2014.8

  A readily accessible catalytic system, PdCl2(Ph3P)(2)/Ph3P, was developed for the selective arylation of primary anilines with aryl bromides. The strong influence of solvents and bases on the catalytic activity was observed. In refluxing o-xylene, triphenylphosphine shows high efficiency for Pd-catalyzed intermolecular amination reactions. By changing the bases, mono- and diarylation of primary amines could be selectively achieved in high yields. Moreover, the catalytic system showed good toleration for the steric hindrance of anilines. A series of N,N,N',N'-tetraaryl-1,1'-biphenyl-4,4'-diamines, important intermediates of OLED hole transport materials, were synthesized facilely via coupling reactions between 4,4'-diaminobiphenyls and aryl bromides. (C) 2014 Elsevier Ltd. All rights reserved.