6'-溴-5-甲基-2,2'-联吡啶 | 189195-36-6

• 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
• 中文名称: 6'-溴-5-甲基-2,2'-联吡啶
• 英文名称: 6-bromo-5'-methyl-2,2'-bipyridine
• 英文别名: 6'-Bromo-5-methyl-2,2'-bipyridine；2-bromo-6-(5-methylpyridin-2-yl)pyridine
• CAS: 189195-36-6
• 化学式: C₁₁H₉BrN₂
• 分子量: 249.11
• InChiKey: QBCBAEQKHOFINO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6'-溴-5-甲基-2,2'-联吡啶 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 四(三苯基膦)钯 potassium acetate 、 potassium carbonate 作用下， 以 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 生成 5-(8-(4-methoxyphenyl)-1,10-phenanthrolin-3-yl)-5''-methyl-2,2':6',2''-terpyridine
  参考文献：
  名称：

  包含直接键合的1,10-菲咯啉和2,2'：6'，2''-叔吡啶单元的新型对位配体的合成

  摘要：

  描述了一种刚性的对位配体的合成，该刚性对位配体包含通过其3位直接连接到2,2'：6'，2''-吡啶的5位的1,10-菲咯啉。合成基于一系列从1,10-菲咯啉和溴取代的吡啶开始的钯（0）催化的交叉偶联反应（Stille和Suzuki偶联）。

  DOI：

  10.1016/j.tetlet.2006.03.025
• 作为产物：
  描述：

  2-溴-5-甲基吡啶 在 四(三苯基膦)钯 正丁基锂 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 生成 6'-溴-5-甲基-2,2'-联吡啶
  参考文献：
  名称：

  包含直接键合的1,10-菲咯啉和2,2'：6'，2''-叔吡啶单元的新型对位配体的合成

  摘要：

  描述了一种刚性的对位配体的合成，该刚性对位配体包含通过其3位直接连接到2,2'：6'，2''-吡啶的5位的1,10-菲咯啉。合成基于一系列从1,10-菲咯啉和溴取代的吡啶开始的钯（0）催化的交叉偶联反应（Stille和Suzuki偶联）。

  DOI：

  10.1016/j.tetlet.2006.03.025

文献信息

• Synthesis, structure, and properties of oligo-tridentate ligands; covalently assembled precursors of coordination arrays
  作者：Garry S. Hanan、Ulrich S. Schubert、Dirk Volkmer、Emmanuel Rivière、Jean-Marie Lehn、Nathalie Kyritsakas、Jean Fischer

  DOI：10.1139/v97-020

  日期：1997.2.1

  Oligo-tridentate ligands based on alternating pyridines and pyrimidines were synthesised by Stille-type carbon–carbon bond-forming reactions. The terpyridine-like sites are designed to coalign upon metal complexation, giving rise to organized and rigidly spaced metal ions. Peripheral functionalization of the basic bis-tridentate framework was explored. The heterocycles in the ligands are in an all-trans conformation about the interannular bonds as indicated by comparison of their ¹H NMR spectra. An X-ray crystal structure analysis of the nonchiral tris-tridentate ligand 2a reveals a helical structure in the solid state. The seven heterocycles form a helical structure with resulting overlap of the terminal pyridines. Their centroid-to-centroid distance is 4.523 Å with 38.8° between the planes. NMR investigations support a helical conformation in solution as well. Electrochemical and UV absorption measurements indicate that the LUMO resides on the pyrimidine moiety of the ligands. Keywords: nitrogen-containing ligands, Stille coupling, helical structure, supramolecular chemistry.

  基于交替的吡啶和嘧啶的寡三齿配体通过Stille型碳-碳键形成反应合成。类似于三吡啶的位点被设计为在金属络合时共线排列，形成有序且刚性间隔的金属离子。探索了对基本双三齿骨架的周边官能化。配体中的杂环在其¹H NMR谱的比较中显示其在环间键周围呈全反构象。非手性三三齿配体2a的X射线晶体结构分析显示在固态中呈螺旋结构。七个杂环形成一个螺旋结构，导致末端吡啶之间的重叠。它们的重心至重心距离为4.523 Å，平面之间的夹角为38.8°。NMR研究也支持在溶液中存在螺旋构象。电化学和紫外吸收测量表明配体的LUMO位于嘧啶部分。关键词：含氮配体，Stille偶联，螺旋结构，超分子化学。
• Facile Synthesis of Polypyridine Esters:  A Route to Functionalized Aldehydes
  作者：Abdelkrim El-ghayoury、Raymond Ziessel

  DOI：10.1021/jo000635g

  日期：2000.11.1

  synthesized and fully characterized. The principal reaction involves the palladium(0)-catalyzed carboalkoxylation of the bromo-, chloro- or triflate-substituted pyridine unit with carbon monoxide in the presence of a primary alcohol as nucleophile and a tertiary amine as base. Monofunctionalization of disubstituted compounds is realized by reaction in ethanol under mild conditions (70 degrees C, 1 atm

  基于吡啶，1,8-萘啶，1,10-菲咯啉，2,2'-联吡啶和2,2'：6'，6''-叔吡啶单元的各种酯取代的低聚吡啶综合和充分表征。主要反应涉及在伯醇为亲核试剂和叔胺为碱的情况下，用一氧化碳对溴，氯或三氟甲磺酸取代的吡啶单元进行钯（0）催化的碳烷氧基化。通过在温和的条件下（70摄氏度，1个大气压的二氧化碳）在乙醇中反应，可以实现双取代化合物的单官能化。用硼氢化钠逐步还原选择的酯，然后进行Swern氧化，以良好的收率得到相应的甲醛。首次报道了几种产品。本文报道的合成方法代表了大规模制备酯官能化的低聚吡啶的有价值的方法，其随后可转化为相应的醇或酸。这些程序也为合理设计带有不同功能的配体提供了一种实用的方法。
• Synthesis of Flexible Polydendate Ligands Bearing 5′-Substituted-6-carboxylic-2,2′-bipyridine Subunits
  作者：Loïc J. Charbonnière、Nicolas Weibel、Raymond F. Ziessel

  DOI：10.1055/s-2002-31968

  日期：——

  6-bromo-5'-bromomethyl-2,2'-bipyridine and acyclic amines or primary alcohol via base-assisted nucleophilic substitutions. In all cases, transformation of the bromo-function to the corresponding ethyl esters has been made possible under mild conditions using a palladium promoted carboethoxylation reaction, while saponification under basic conditions provided the corresponding acids after protonation. The utility of

  研究了不对称5',6-二取代-2,2'-联吡啶在制备柔性多主题配体中的合成范围。关键的 6-bromo-5'-bromomethyl-2,2'-bipyridine 结构单元的制备涉及 Krohnke 方案，然后是经过优化的自由基溴化反应。6-bromo-5'-bromomethyl-2,2'-bipyridine 的功能化已经通过 Delepine 和 Gabriel 反应实现，水解后提供相应的氨基化合物，而醋酸盐的亲核攻击随后皂化反应提供相应的酒精。多官能化联吡啶配体已通过碱辅助亲核取代从 6-bromo-5'-bromomethyl-2,2'-bipyridine 和无环胺或伯醇一步制备。在所有情况下，在温和的条件下，使用钯促进的乙氧基化反应使溴官能团转化为相应的乙酯成为可能，而碱性条件下的皂化在质子化后提供相应的酸。本文报道的协议的效用已扩展到乙二胺平台的合成，该平台带有附加的 4-硝基苄基，用于潜在地连接到其他分子。
• 5‘-Substituted-6-carboxylic-2,2‘-bipyridine Acid:  A Pivotal Architecton for Building Preorganized Ligands
  作者：Loïc J. Charbonnière、Nicolas Weibel、Raymond F. Ziessel

  DOI：10.1021/jo0200015

  日期：2002.5.1

  A set of ligands bearing 6-bromo-2,2'-bipyridine pendant arms attached in the 5'-position are described. Trans formation of the bromo to an ester was performed by a carboethoxylation reaction promoted by low-valent Pd(0), while saponification followed by acidification gave the acids. The introduction of an appended function 3-nitrobenzyl, benzamidomethyl, and tert-butylacetyl opens the way to further functionalize these scaffolds for potential labeling of biological material. The synthetic protocols represent a valuable approach to the rational design of ligands bearing oxophilic and anionic sidearms.
• Synthesis of mono-, bis- and tris-tridentate ligands based on 5′-substituted-2,2′-bipyridine-6-carboxylic acid
  作者：Loı̈c J Charbonnière、Nicolas Weibel、Raymond F Ziessel

  DOI：10.1016/s0040-4039(00)02033-5

  日期：2001.1

  The synthesis of 5'-methyl-2,2'-bipyridine-6-carboxylic acid is described starting from the pivotal 5'-methyl-6-bromo-2,2'-bipyridine building block. Functionalisation of the latest at the 5'-methyl position gives access to the 5'-bromomethyl, 5'-hydroxymethyl and 5'-aminomethyl derivatives. Upon nucleophilic substitution, the hydroxy and amino derivatives react with the 5'-bromomethyl compound to give quasi-linear and podand type intermediates. Thanks to a carboalkoxylation reaction at the 6-bromo position of the different intermediates, followed by a saponification reaction, mono-, bis- and tris-tridentate ligands are obtained, which are particularly well suited for the complexation of lanthanide(III) cations. (C) 2001 Elsevier Science Ltd. All rights reserved.