2-[(4-甲基苯基)亚氨基甲基]苯胺 | 55857-35-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 2-[(4-甲基苯基)亚氨基甲基]苯胺
• 英文名称: 2-aminobenzylidene-p-tolylamine
• 英文别名: 2-[(4-Methylphenyl)iminomethyl]aniline
• CAS: 55857-35-7
• 化学式: C₁₄H₁₄N₂
• 分子量: 210.279
• InChiKey: PFPHLBCPQWNXNZ-UHFFFAOYSA-N

物化性质

• 熔点：
  102-103 °C
• 沸点：
  385.8±35.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  38.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-[(4-甲基苯基)亚氨基甲基]苯胺 在 sodium carbonate 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 27.5h， 生成 ethyl 1-methyl-2-phenyl-4-(piperidin-1-yl)-1,4-dihydroquinoline-3-carboxylate
  参考文献：
  名称：

  Preparation of axially chiral quinolinium salts related to NAD+ models: new investigations of these biomimetic models as ‘chiral amide-transferring agents’

  摘要：

  The general purpose of this work is to investigate the potential of biomimetic NAD(+) models as 'nucleophile-transferring agents' with the ultimate motivation to develop new synthetic tools. This first report focuses on the preparation of an axially chiral quinolinium salt 8. A preliminary investigation of these NAD(+) analogues as 'chiral amide-transferring agents' is reported herein. The synthesis of the desired quinolinium salt 8 was first attempted via a Friedlander approach. Given the poor reproducibility of this first synthetic route, a second strategy making use of an intramolecular nickel-catalyzed coupling was developed with success, furnishing the quinolinium salt 8 in 12% overall yield. The potential of the quinolinium salt 8 as a 'chiral amide-transferring agent' was then investigated. Regioselective 1,4-addition of benzylamine and piperidine produced, respectively, adducts 18a and 18b with high diastereoselectivity (de >95%). The resulting 'chiral masked-amide' 18b was reacted with various activated aryl esters affording the corresponding atropisomeric amide 20 with modest atropenantioselectivity (ee = 2-20%). (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.11.004
• 作为产物：
  描述：

  N-(2-硝基苯亚甲基)对甲苯胺 在 sodium sulfide 作用下， 以 乙醇 为溶剂， 反应 0.17h， 以80%的产率得到2-[(4-甲基苯基)亚氨基甲基]苯胺
  参考文献：
  名称：

  Preparation of axially chiral quinolinium salts related to NAD+ models: new investigations of these biomimetic models as ‘chiral amide-transferring agents’

  摘要：

  The general purpose of this work is to investigate the potential of biomimetic NAD(+) models as 'nucleophile-transferring agents' with the ultimate motivation to develop new synthetic tools. This first report focuses on the preparation of an axially chiral quinolinium salt 8. A preliminary investigation of these NAD(+) analogues as 'chiral amide-transferring agents' is reported herein. The synthesis of the desired quinolinium salt 8 was first attempted via a Friedlander approach. Given the poor reproducibility of this first synthetic route, a second strategy making use of an intramolecular nickel-catalyzed coupling was developed with success, furnishing the quinolinium salt 8 in 12% overall yield. The potential of the quinolinium salt 8 as a 'chiral amide-transferring agent' was then investigated. Regioselective 1,4-addition of benzylamine and piperidine produced, respectively, adducts 18a and 18b with high diastereoselectivity (de >95%). The resulting 'chiral masked-amide' 18b was reacted with various activated aryl esters affording the corresponding atropisomeric amide 20 with modest atropenantioselectivity (ee = 2-20%). (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.11.004

文献信息

• A General Cp*Co^III-Catalyzed Intramolecular C−H Activation Approach for the Efficient Total Syntheses of Aromathecin, Protoberberine, and Tylophora Alkaloids
  作者：Andreas Lerchen、Tobias Knecht、Maximilian Koy、Constantin G. Daniliuc、Frank Glorius

  DOI：10.1002/chem.201702648

  日期：2017.9.7

  Herein, we report a Cp*CoIII‐catalyzed C−H activation approach as the key step to create highly valuable isoquinolones and pyridones as building blocks that can readily be applied in the total syntheses of a variety of aromathecin, protoberberine, and tylophora alkaloids. This particular C−H activation/annulation reaction was achieved with several terminal as well as internal alkyne coupling partners

  在此，我们报告Cp * Co III催化的C H活化方法是创建高度有价值的异喹诺酮和吡啶酮的重要步骤，这些异喹啉酮和吡啶酮可以轻松地用于各种芳香族素，原小ber碱和tylophora生物碱的总合成。这种特殊的CH活化/环化反应是通过多个末端以及内部炔烃偶联伙伴实现的，具有广泛的应用范围和出色的官能团耐受性。本文报道的该方案的合成适用性已在两个Topo-I-抑制剂和两个8-氧代小ber碱核心的合成中得到了证明，这些核心可进一步制成四氢小ber碱和原小ber碱生物碱。此外，这些构件也以方便的方式转化为六种不同的tylophora生物碱。
• Total Synthesis of (+)-Camptothecin via an Intramolecular Palladium-Catalyzed Cyclization Strategy
  作者：Subhash Chavan、Ashok Pathak、Uttam Kalkote

  DOI：10.1055/s-2007-991054

  日期：——

  The novel cascade intramolecular Pd-catalyzed cyclization followed by aromatization for the construction of d ring of (+)-camptothecin as a key step is demonstrated.

  研究表明，构建(+)-喜树碱D环的关键步骤是一种新颖的分子内Pd催化的级联环化反应，随后进行芳香化作用。
• Rhodium(III)-Catalyzed Intramolecular Annulation through CH Activation: Total Synthesis of (±)-Antofine, (±)-Septicine, (±)-Tylophorine, and Rosettacin
  作者：Xianxiu Xu、Yu Liu、Cheol-Min Park

  DOI：10.1002/anie.201204970

  日期：2012.9.10

  Annulation: The efficient synthesis of 3‐hydroxyalkyl isoquinolones and 6‐hydroxyalkyl 2‐pyridones is enabled through the intramolecular annulation of alkyne‐tethered hydroxamic esters (see scheme, Cp*=pentamethylcyclopentadienyl). The reaction features high regioselectivity, broad substrate scope, and excellent functional‐group tolerance, proceeds under mild reaction conditions with low catalyst loading

  注释：通过炔烃系异羟肟酸酯的分子内环化，可实现3-羟基烷基异喹诺酮和6-羟基烷基2-吡啶酮的高效合成（参见方案，Cp * =五甲基环戊二烯基）。该反应具有较高的区域选择性，广泛的底物范围和出色的官能团耐受性，可在温和的反应条件下以较低的催化剂负载量进行，并且无需外部氧化剂。
• Cobalt-Catalyzed Oxidase C−H/N−H Alkyne Annulation: Mechanistic Insights and Access to Anticancer Agents
  作者：Ruhuai Mei、Hui Wang、Svenja Warratz、Stuart A. Macgregor、Lutz Ackermann

  DOI：10.1002/chem.201601101

  日期：2016.5.10

  Cp*‐free cobalt‐catalyzed alkyne annulations by C−H/N−H functionalizations were accomplished with molecular O2 as the sole oxidant. The user‐friendly oxidase strategy proved viable with various internal and terminal alkynes through kinetically relevant C−H cobaltation, providing among others step‐economical access to the anticancer topoisomerase‐I inhibitor 21,22‐dimethoxyrosettacin. DFT calculations

  通过CH / N-H官能化的无Cp *钴催化的炔烃环化反应以分子O 2为唯一氧化剂完成。用户友好的氧化酶策略通过动力学相关的C-H钴化被证明对各种内部和末端炔烃都是可行的，除其他步骤外，经济实用地获得了抗癌拓扑异构酶I抑制剂21,22-dimethoxyrosettacin。DFT计算表明，电子效应控制了炔烃插入步骤的区域选择性。
• Cerium(IV) Ammonium Nitrate Is an Excellent, General Catalyst for the Friedländer and Friedländer−Borsche Quinoline Syntheses: Very Efficient Access to the Antitumor Alkaloid Luotonin A
  作者：Vellaisamy Sridharan、Pascual Ribelles、M Teresa Ramos、J. Carlos Menéndez

  DOI：10.1021/jo900965f

  日期：2009.8.7

  The use of cerium(IV) ammonium nitrate as a catalyst of the Friedländer reaction allows the synthesis of polysubstituted quinoline derivatives in excellent yields, avoiding the traditional harshly basic or acidic conditions. Unlike most other previously known reagents, CAN allows double condensations and is also an excellent catalyst for the Borsche variation of the Friedländer reaction, which has

  使用硝酸铈（IV）铵作为Friedländer反应的催化剂，可以以优异的收率合成多取代的喹啉衍生物，从而避免了传统的苛刻的碱性或酸性条件。与大多数其他先前已知的试剂不同，CAN允许双重缩合，并且还是Friedländer反应的Borsche变体的极佳催化剂，该反应已被用于非常有效地合成抗肿瘤生物碱褪黑素A。