ethyl 5'-methyl-6-(2,2'-bipyridine)carboxylate | 314767-95-8

• 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: ethyl 5'-methyl-6-(2,2'-bipyridine)carboxylate
• 英文别名: ethyl 5'-methyl-2,2'-bipyridine-6-carboxylate；6-carboethoxy-5'-methyl-2,2'-bipyridine；Ethyl 6-(5-methylpyridin-2-yl)pyridine-2-carboxylate
• CAS: 314767-95-8
• 化学式: C₁₄H₁₄N₂O₂
• 分子量: 242.277
• InChiKey: ZSTJOYCGIYOURU-UHFFFAOYSA-N

物化性质

• 沸点：
  409.2±45.0 °C(Predicted)
• 密度：
  1.143±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  52.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 5'-methyl-6-(2,2'-bipyridine)carboxylate 在 溴 作用下， 以 水 、 苯 为溶剂， 反应 0.5h， 以73%的产率得到ethyl 5'-bromomethyl-6-(2,2'-bipyridine)-carboxylate
  参考文献：
  名称：

  Carboxylate Derivatives of Oligopyridines Bearing Bromomethyl Groups

  摘要：

  本研究报道了多种具有一个羧基和至少一个溴乙基的低聚吡啶的合成。双吡啶和terpyridine 核心是通过 Stille 交叉偶联法，从溴邻吡啶和溴邻吡啶甲酸乙酯开始，以良好的收率合成的。溴甲基官能团是通过在苯中使用 NBS 或在苯/水双相混合物中使用溴进行自由基溴化得到的。文中介绍了通过胺或苯酚基团对苄基溴的亲核置换作用建立两种模型荚膜的方法。

  DOI：

  10.1055/s-2002-33347
• 作为产物：
  描述：

  2-溴-6-甲基吡啶 在 chromium(VI) oxide 、 正丁基锂 、 硫酸 作用下， 以 四氢呋喃 、 硫酸 为溶剂， 反应 48.0h， 生成 ethyl 5'-methyl-6-(2,2'-bipyridine)carboxylate
  参考文献：
  名称：

  Synthesis of bisfunctionalized-oligopyridines bearing an ester group

  摘要：

  The synthesis of 2,2 ' -bipyridine, 1,10-phenantroline and 2,2 ' :6 ' ,2 " -terpyridine substituted by an ethylester function is described. The 5- and 6-methyl-2,2 ' -bipyridines bearing an ethylester group on the 6 ' position as well as the ethyl 6,6 " -dimethyl-2,2 ' :6 ' ,2 " -terpyridine-4 ' -carboxylate moiety were synthesized via a Stille cross-coupling reaction, starting from bromo-picoline building blocks. A radical bromination of the methyl-oligopyridine gave selectively the corresponding benzylic bromide derivatives in fair yield. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01195-9

文献信息

• 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。
• Synthesis, characterization and crystal structure of bis(5′-methyl-2,2′-bipyridine-6-carboxylato) ruthenium(II)
  作者：Athanassios I. Philippopoulos、Evangelia Chatzivasiloglou、Aris Terzis、Catherine P. Raptopoulou、Pierre Tisnès、Claude Picard、Polycarpos Falaras

  DOI：10.1016/j.inoche.2004.11.027

  日期：2005.2

  Abstract A homoleptic ruthenium(II) complex with the ligand (5′-methyl-2,2′-bipyridine-6-carboxylate) has been prepared and characterized by elemental analysis, FT-IR, 1H, 13C NMR 1D and 2D and electronic absorption spectroscopy. The X-ray crystal structure of the complex has also been determined. It crystallizes in the triclinic crystal system space group P 1 ¯ , exhibiting a distorted octahedral

  摘要 制备了配体（5'-甲基-2,2'-联吡啶-6-羧酸酯）的均配钌（II）配合物，并通过元素分析、FT-IR、1H、13C NMR 1D和2D以及电子吸收光谱。复合物的 X 射线晶体结构也已确定。它在三斜晶系空间群 P 1 ¯ 中结晶，在钌原子周围表现出扭曲的八面体几何形状。
• 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.