N-(3-bromo-5-chloropyridin-2-yl)pyridin-1-ium-1-aminide | 171774-38-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: N-(3-bromo-5-chloropyridin-2-yl)pyridin-1-ium-1-aminide
• 英文别名: (3-Bromo-5-chloropyridin-2-yl)-pyridin-1-ium-1-ylazanide
• CAS: 171774-38-2
• 化学式: C₁₀H₇BrClN₃
• 分子量: 284.543
• InChiKey: INBVKZAQKADLNW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(3-bromo-5-chloropyridin-2-yl)pyridin-1-ium-1-aminide 在 四(三苯基膦)钯 、 potassium carbonate 、 溶剂黄146 、 锌 作用下， 以 乙醇 、 甲苯 为溶剂， 反应 41.0h， 生成 5-chloro-3-(4-methylsulfonylphenyl)-2-pyridinamine
  参考文献：
  名称：

  A facile synthesis of 3,5-halo and aryl 1H-pyridin-2-ones from pyridinium N-(pyridin-2-yl)aminide

  摘要：

  The synthesis of halogenated and arylated 1H-pyridin-2-ones starting from pyridinium N-(pyridin-2-yl)aminides is described. The synthetic pathway involves the reaction of pyridinium N-(5-bromopyridin-2-yl)aminide, N-(3-bromo-5-chloropyridin-2-yl)aminide or N-(3,5-dibromopyridin-2-yl)aminide with different boronic acids to afford monosubstituted and disubstituted aminides in good yields. An additional bromination in the 3-position of N-(5-arylpyridin-2-yl)aminides was performed. Finally, reduction of the N-N bond followed by the reaction of the corresponding 2-aminopyridines with sodium nitrite/sulfuric acid in water yields 3,5-disubstituted 1H-pyridin-2-ones in good yields. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.05.065
• 作为产物：
  描述：

  pyridinium N-(2'-pyridyl)aminide 在 N-氯代丁二酰亚胺 、 N-溴代丁二酰亚胺(NBS) 作用下， 以 二氯甲烷 为溶剂， 生成 N-(3-bromo-5-chloropyridin-2-yl)pyridin-1-ium-1-aminide
  参考文献：
  名称：

  N-Azinylpyridinium N-Aminides：一种通过分子内自由基途径制备吡唑并吡啶的方法

  摘要：

  描述了分子内自由基芳基化，在热条件下，连接到过量的 2-azinyliminopyridine 部分的 - 缺陷的吡啶鎓。该方法允许新进入吡唑并(1,5-a)吡啶核。使用三正丁基氢化锡 (Bu3SnH) 和偶氮二异丁腈 (AIBN) 衍生自芳基卤化物的芳基自由基的生成和后续反应现已得到充分记录，并且已经报道了几种基于芳基自由基环化的合成。1 杂芳基的几个例子是已知的，据推测它们的行为与芳基相似，因为孤电子将位于与芳族系统正交的轨道上，因此，它的性质（-过量或-不足）应该具有对这些自由基的反应性影响很小或没有影响。2 特别关注吡啶基；Snieckus 3 和 Nadin 4 都报道了吡啶基自由基环化。Harrowven 5 发表了一些论文，其中包括吡啶基环化和芳基环化到吡啶上。Jones 6 公开了使用衍生自 3-溴吡啶的自由基，并将这种化学扩展到吡啶鎓自由基。7 然而，据我们所知，之前还没有报道过吡嗪基自由基环化。

  DOI：

  10.1055/s-2002-32596

文献信息

• Pyridinium N-2′-pyridylaminide: radical cyclization in the synthesis of annulated 2-aminopyridines
  作者：Aránzazu Sánchez、Araceli Núñez、Carolina Burgos、Julio Alvarez-Builla

  DOI：10.1016/j.tetlet.2006.09.092

  日期：2006.11

  The synthesis of annulated 2-aminopyridines by intramolecular radical pyridylation of the appropriate substrates, obtained from pyridinium N-2′-pyridylaminide, can be performed using TTMSS and AIBN.

  可以使用TTMSS和AIBN通过适当的底物的分子内自由基吡啶基化来合成环状的2-氨基吡啶，所述底物是由吡啶鎓N -2'-吡啶基酰亚胺获得的。
• Pyridinium N-2′-pyridylaminide: synthesis of 3-aryl-2-aminopyridines through an intramolecular radical process
  作者：Aránzazu Sánchez、Araceli Núñez、Julio Alvarez-Builla、Carolina Burgos

  DOI：10.1016/j.tet.2004.09.099

  日期：2004.12

  Tris(trimethylsilyl)silane (TTMSS) and azobisisobutironitrile (AIBN) promote the intramolecular heteroarylation of arenesulfonamides with pyridyl radicals under thermal conditions. The arenesulfonamides are easily prepared from pyridinium N-2′-pyridylaminide. The heteroarylation process involves pyridyl radical cyclization and ipso substitution.

  三（三甲基甲硅烷基）硅烷（TTMSS）和偶氮二异丁腈（AIBN）在热条件下促进芳族磺酰胺与吡啶基的分子内杂芳基化。芳族磺酰胺很容易从吡啶鎓N -2'-吡啶酰胺制备。杂芳基化过程涉及吡啶基自由基环化和ipso取代。
• Unusual Approach to 3-Aryl-2-aminopyridines through a Radical Mechanism: Synthesis and Theoretical Rationale from Quantum Mechanical Calculations
  作者：Marta Camacho-Artacho、Valentina Abet、Luis M. Frutos、Federico Gago、Julio Alvarez-Builla、Carolina Burgos

  DOI：10.1021/jo102122h

  日期：2011.3.4

  Tris(trimethylsilyl)silane and azobis(cyclohexanenitrile) promoted the easy intramolecular arylation of aryl bromopyridine carbamates through a radical [1,6] ipso substitution process. These substrates showed a preference for this type of reaction over the alternative [1,7] addition. The results were rationalized by making use of quantum mechanical calculations and computer graphics.
• A New Class of Pyrazolopyridine Nucleus with Fluorescent Properties, Obtained through Either a Radical or a Pd Arylation Pathway from <i>N</i>-Azinylpyridinium <i>N</i>-Aminides
  作者：Valentina Abet、Araceli Nuñez、Francisco Mendicuti、Carolina Burgos、Julio Alvarez-Builla

  DOI：10.1021/jo801549u

  日期：2008.11.21

  The synthesis of dipyridopyrazole and pyridopyrazolopyrazine derivatives--both of which incorporate a 3-aryl moiety--can be achieved in moderate yields by intramolecular radical arylation of pyridinium N-aminides using tris(trimethylsilyl)silane and azobisisobutyronitrile. Improved results were obtained on using Pd direct arylation in conjunction with microwave irradiation. A preliminary study into the fluorescent properties of the target compounds is also reported.
• Halogenation of pyridinium-N-(2′-pyridyl)aminide: An easy synthesis of halo-2-aminopyridines
  作者：Carolina Burgos、Francisca Delgado、J. Luis García-Navío、M. Luisa Izquierdo、Julio Alvarez-Builla

  DOI：10.1016/0040-4020(95)00478-q

  日期：1995.7

  The regioselective halogenation of pyridinium-N-(2'-pyridyl)aminide 1 with N-chloro, bromo or iodosuccinimide under mild conditions is described. The method, combined with a reduction of the N-N bond, allows an easy preparation of 5-halo and 3,5-dihalo-2-aminopyridines 4.