3,5-dimethyl-N-p-tolylbenzenamine | 34160-16-2

• 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: 3,5-dimethyl-N-p-tolylbenzenamine
• 英文别名: 3,5-dimethyl-N-p-tolylaniline；N-(4-Methylphenyl)-3,5-dimethylaniline；3,5,4'-Trimethyl-diphenylamin；3,5-dimethyl-N-(4-methylphenyl)aniline
• CAS: 34160-16-2
• 化学式: C₁₅H₁₇N
• 分子量: 211.307
• InChiKey: ZSPLMPHPCGAXSC-UHFFFAOYSA-N

物化性质

• 沸点：
  339.6±11.0 °C(Predicted)
• 密度：
  1.034±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  5-硝基间二甲苯 在 bis(acetylacetonato)palladium(II) 、 2-(二环己基膦)3,6-二甲氧基-2′,4′,6′-三异丙基-1,1′-联苯 、 四丁基溴化铵 、 caesium carbonate 、 联硼酸频那醇酯 作用下， 以 甲苯 为溶剂， 反应 40.0h， 生成 3,5-dimethyl-N-p-tolylbenzenamine
  参考文献：
  名称：

  硝基芳烃作为亲电子试剂和芳胺替代物在 Buchwald-Hartwig 型 C-N 键构建偶联中的双重作用

  摘要：

  构建 C(sp 2 )–N 键最广泛使用的方法之一是过渡金属催化的芳基卤化物/硼酸与胺的交叉偶联，称为乌尔曼缩合、Buchwald-Hartwig 胺化和 Chan –拉姆联轴器。然而，芳基卤化物/硼酸通常需要多步制备，同时产生大量腐蚀性和有毒废物，使得该反应不太有吸引力。在此，我们提出了一种前所未有的方法，通过Buchwald-Hartwig 型反应形成 C(sp 2 )–N，使用合成上游硝基芳烃作为唯一起始原料，从而消除了对芳基卤化物和预先形成的芳基胺的需要。从硝基芳烃一步获得了多种对称的二芳基胺和三芳基胺，更重要的是，还通过一锅/两步法高选择性地合成了各种不对称的二芳基胺和三芳基胺。此外，放大实验的成功、药物中间体的后期功能化以及空穴传输材料TCTA的快速制备展示了该方案在合成化学中的实用性和实用性。机理研究表明，这种转化可能通过硝基芳烃还原原位生成的芳胺中间体进行，随后与另一种硝基芳烃发生脱硝

  DOI：

  10.1039/d3sc06618e

文献信息

• Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds
  申请人：——

  公开号：US20030065187A1

  公开（公告）日：2003-04-03

  The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide or amine moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In additional embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between a nitrogen atom of an acyl hydrazine and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of a nitrogen-containing heteroaromatic, e.g., indole, pyrazole, and indazole, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-oxygen bond between the oxygen atom of an alcohol and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. The present invention also relates to copper-catalyzed methods of forming a carbon-carbon bond between a reactant comprising a nucleophilic carbon atom, e.g., an enolate or malonate anion, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. Importantly, all the methods of the present invention are relatively inexpensive to practice due to the low cost of the copper comprised by the catalysts.

  本发明涉及铜催化的碳-杂原子和碳-碳键形成方法。在某些实施例中，本发明涉及铜催化的方法，用于在酰胺或胺基团的氮原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氮键。在其他实施例中，本发明涉及铜催化的方法，用于在酰基肼的氮原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氮键。在另一些实施例中，本发明涉及铜催化的方法，用于在含氮杂环芳烃（例如吲哚、吡唑和吲哌）的氮原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氮键。在某些实施例中，本发明涉及铜催化的方法，用于在醇的氧原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氧键。本发明还涉及铜催化的方法，用于在包含亲核碳原子的反应物（例如烯醇酸盐或丙二酸盐负离子）与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-碳键。重要的是，由于催化剂中铜的低成本，本发明的所有方法都相对廉价。
• Well-Designed <i>N</i>-Heterocyclic Carbene Ligands for Palladium-Catalyzed Denitrative C–N Coupling of Nitroarenes with Amines
  作者：Wei Chen、Kai Chen、Wanzhi Chen、Miaochang Liu、Huayue Wu

  DOI：10.1021/acscatal.9b02760

  日期：2019.9.6

  the low reactivity of the Ar–NO2 bond toward oxidative addition. We report here the C–N coupling of nitroarenes and amines using palladium/5-(2,4,6-triisopropylphenyl)imidazolylidene[1,5-a]pyridines as the catalyst. The ligands are readily available from commercial chemicals. The reaction shows broad substrate scope and functional group tolerance. The method is applicable to both aromatic and aliphatic

  C–N键的形成是有机化学中的基本反应之一，因为药物和生物活性化合物中胺基的广泛存在。钯催化卤代芳烃的CN偶联是芳族胺最有效的方法之一。硝基芳烃价格低廉且易于获得，因此是理想的替代亲电偶联伙伴。使用硝基芳烃作为亲电子伴侣的脱硝和交叉偶联具有挑战性，因为Ar-NO 2键对氧化加成的反应性较低。我们在这里报告使用钯/ 5-（2,4,6-三异丙基苯基）咪唑基亚甲基[1,5- a以吡啶为催化剂。配体可容易地从商业化学品获得。该反应显示出广泛的底物范围和官能团耐受性。该方法适用于芳族和脂族胺，并且以高收率获得了带有各种官能团的许多仲和叔芳族胺。
• Efficient Iron/Copper Cocatalyzed N-Arylation of Arylamines with Bromoarenes
  作者：Songlin Zhang、Xiaoyan Liu

  DOI：10.1055/s-0030-1260534

  日期：2011.5

  Fe(acac)3 and Cu(OAc)2×H2O were found to effectively promote the C-N cross-coupling reaction in the presence of K2CO3 as the base. A series of diaryl amine with different substituents can be synthesized in moderate to good yields. This efficient and economic method is attractive for applications on an industrial scale.

  研究发现，Fe(acac)3和Cu(OAc)2×H2O在K2CO3作为碱的存在下，能有效促进C-N交叉偶联反应。一系列具有不同取代基的二芳基胺可以在中等到良好的产率下合成。这种高效且经济的方法对于工业规模的应用具有吸引力。
• Electrochemical Reductive Arylation of Nitroarenes with Arylboronic Acids
  作者：Dan Wang、Zhaohua Wan、Heng Zhang、Hesham Alhumade、Hong Yi、Aiwen Lei

  DOI：10.1002/cssc.202101924

  日期：2021.12.17

  Reductive arylation: The synthesis of diarylamine is extremely important in organic chemistry. Herein, a novel electrochemical reductive arylation of arylboronic acids with nitroarenes is developed. A variety of diarylamines is synthesized without the need for transition-metal catalysts. The reaction can be scaled up efficiently in a flow cell and several derivatization reactions are carried out smoothly

  还原芳基化：二芳基胺的合成在有机化学中极为重要。在此，开发了芳基硼酸与硝基芳烃的新型电化学还原芳基化。无需过渡金属催化剂即可合成多种二芳基胺。该反应可以在流动池中有效放大，并且几个衍生反应可以顺利进行。
• Buchwald-Hartwig Amination of (Hetero)aryl Chlorides by Employing Mor-DalPhos under Aqueous and Solvent-Free Conditions
  作者：Bennett J. Tardiff、Mark Stradiotto

  DOI：10.1002/ejoc.201200510

  日期：2012.7

  catalyst system in the Buchwald–Hartwig amination of (hetero)aryl chlorides with primary or secondary amines conducted either under aqueous conditions without the use of co-solvents and/or surfactants or under solvent-free conditions (52 examples). We have established that reactions of this type can be conducted without the rigorous exclusion of air, and in the case of the solvent-free reactions, we have

  我们报告了 [Pd(cinnamyl)Cl]2/Mor-DalPhos 催化剂体系在（杂）芳基氯化物与伯胺或仲胺的 Buchwald-Hartwig 胺化中的应用，该胺化反应在水性条件下进行，不使用共溶剂和/或表面活性剂或在无溶剂条件下（52 个例子）。We have established that reactions of this type can be conducted without the rigorous exclusion of air, and in the case of the solvent-free reactions, we have demonstrated that appropriately selected liquid and solid reagents can be employed successfully.