2,2'-联吡啶-6-甲酸甲酯 | 203573-76-6

• 物质功能分类: 医药中间体 - 吡啶类化合物
• 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: 2,2'-联吡啶-6-甲酸甲酯
• 英文名称: 2,2'-dipyridyl-6-carboximidic acid methyl ester
• 英文别名: methyl [2,2′-bipyridin]-6-carboxylate；6-(2,2′-bipyridyl)methylcarboxylate；6-methoxycarbonyl-2,2′-bipyridine；methyl [2,2'-bipyridine]-6-carboxylate；methyl 2,2'-bipyridine-6-carboxylate；methyl-2,2'-bipyridine-6-carboxylate；methyl 6-pyridin-2-ylpyridine-2-carboxylate
• CAS: 203573-76-6
• 化学式: C₁₂H₁₀N₂O₂
• 分子量: 214.224
• InChiKey: QBISCYBGKUJHRG-UHFFFAOYSA-N

物化性质

• 熔点：
  162-163 °C
• 沸点：
  387.3±32.0 °C(Predicted)
• 密度：
  1.196±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 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：

  2,2'-联吡啶-6-甲酸甲酯 在 sodium tetrahydroborate 、 氯化亚砜 、 硫酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 34.0h， 生成 2-(6-Pyridin-2-ylpyridin-2-yl)acetonitrile
  参考文献：
  名称：

  Regioselective Functionalization of 2,2'-Bipyridine and Transformations into Unsymmetric Ligands for Coordination Chemistry.

  摘要：

  Novel synthetic strategies for a series of unsymmetrically substituted 2,2'-bipyridines have been developed. These bipyridines have found use in some novel homoleptic and heteroleptic ruthenium(II) complexes. Two methods for regiochemical control of nucleophilic addition to bpy have been explored: (i) mono N-oxidation followed by cyanation and subsequent hydrolysis gave 6-carboxy-2,2'-bipyridine (4); (ii) mono N-methylation followed by the conversion into 6-bromo-2,2'-bipyridine (12) and subsequent nucleophilic addition of lithio-acetonitrile followed by hydrolysis of 6-cyanomethyl-2,2'-bipyridine (8) gave the homologous 2,2'-bipyridine-6-acetic acid (9). An established method of regioselective mono-ring alkylation of bpy using methyllithium yielded 6-methyl-2,2'-bipyridine (14), and the generation of the anion of 14 and subsequent addition to a chloromethyl oxazoline was applied to synthesize a second homologue, methyl 2,2'-bipyridine-6-propanoate (16). Structural determinations using H-1, C-13 and 2D NMR spectroscopy permitted complete assignments of all signals in the H-1 NMR spectra.

  DOI：

  10.3891/acta.chem.scand.52-0077
• 作为产物：
  描述：

  2,2′-二吡啶基 N-氧化物 在 sodium methylate 、 苯甲酰氯 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 2,2'-联吡啶-6-甲酸甲酯
  参考文献：
  名称：

  芘附加的联吡啶腙配体作为Cu2+的开启传感器及其生物成像应用

  摘要：

  合成了一种芘附加的联吡啶腙基配体HL，并通过光谱方法对其进行了表征。HL与Cu( II )络合后，通过自组装形成具有高缔合常数的六核桨轮金属-有机大环(MOM) ，分子式为[Cu 6 L 6 (NO 3 ) 6 ]。在这种六核 Cu( II ) 配合物中证明了分子间和分子内 π-π 相互作用。此外，观察到HL有可能检测到痕量的 Cu( II) 离子在生理 pH 下的水性介质中的各种生物相关金属离子中选择性地进行。HL具有良好的细胞渗透性和生理条件下的高溶解度以及较高的IC 50值，可以检测活细胞中的铜（II ）离子。低检测限、高灵敏度和良好的重现性使这种铜传感器非常有前景。基于荧光滴定法，发现配体与Cu( II )之间形成的络合物(MOM)为1:1，并通过ESI-MS确认。此外，六核自组装荧光物质的单晶研究提供了对其化学性质的更好了解，例如配位环境和结合模式，不像大多数金属传感器，由于金属

  DOI：

  10.1039/c9ra09376a

文献信息

• Synthesis of 2,2′-Bipyridines via Suzuki-Miyaura Cross-Coupling
  作者：Arne Lützen、Christoph Gütz

  DOI：10.1055/s-0029-1217082

  日期：2010.1

  For a long time, the Suzuki-Miyaura cross-coupling reaction could not be used for the synthesis of 2,2′-bipyridines due to the lack of sufficiently stable 2-pyridylboron compounds. Stabilized 2-pyridylboronic acid esters recently developed by Hodgson, however, were found to be ideally suited for this purpose. Two general protocols could be developed and demonstrated to be valuable alternatives, which

  长期以来，由于缺乏足够稳定的2-吡啶基硼化合物，Suzuki-Miyaura交叉偶联反应无法用于2,2'-联吡啶的合成。然而，发现霍奇森最近开发的稳定的2-吡啶基硼酸酯是理想地适合于此目的的。可以开发出两种通用方案，并证明它们是有价值的替代方案，可以非常有效地用于官能化2，2'-联吡啶的合成。 交叉偶联反应-联吡啶-钯-2-吡啶基硼酸酯-铃木宫浦反应
• Insights on the synthesis and organisational phenomena of twisted pyrazine–pyridine hybrids
  作者：Fenton Heirtzler、Markus Neuburger、Klaus Kulike

  DOI：10.1039/b107751a

  日期：2002.3.8

  Pyrazine–pyridine hybrids containing two different oligopyridyl chains, 2,3-disubstituted onto the pyrazine ring nucleus are prepared from appropriate mixed α-diketone precursors. The latter were obtained by epoxidation of the enols of corresponding 1,2-disubstituted ethanones. The structures of the pyrazine derivatives were investigated by detailed proton NMR spectroscopic and X-ray crystallographic methods. These indicated a twisting of the oligopyridyl chains about one another to result in a pre-double helical topology. This phenomenon occurred up to two pyridin-2,6-diyl groupings from the pyrazine ring and is accompanied by edge-on-face stacking of spatially proximate pyridyl rings. Parallel stacking of pyrazine and weak C–H⋯N acid interactions are significant in their crystal lattices and may also figure in their metallosupramolecular self-assembly behaviour patterns.

  通过适当的混合α-二酮前体，制备了含有两种不同寡吡啶链的吡嗪-吡啶杂化物，这些杂化物在吡嗪环核上进行2,3-二取代。后者是通过相应1,2-二取代乙酮的烯醇的环氧化反应获得的。通过详细的质子核磁共振光谱学和X射线晶体学方法研究吡嗪衍生物的结构。这些研究表明寡吡啶链相互扭曲，形成预双螺旋拓扑结构。这种现象发生在距离吡嗪环最多两个吡啶-2,6-二基基团处，并伴随着空间上接近的吡啶环的边缘面对堆积。吡嗪的平行堆积和弱的C-H…N酸性相互作用在其晶格中具有重要意义，并可能在其金属超分子自组装行为模式中发挥作用。
• Ruthenium complexes bearing an unsymmetrical pincer ligand with a 2-hydroxypyridylmethylene fragment: active catalysts for transfer hydrogenation of ketones
  作者：Jing Shi、Bowen Hu、Dawei Gong、Shu Shang、Guangfeng Hou、Dafa Chen

  DOI：10.1039/c6dt00034g

  日期：——

  Five ruthenium(II) complexes were synthesized, including (HO-C5H3N-CH2-C5H3N-C5H4N)Ru(PPh3)Cl2 (3), [(HO-C5H3N-CH2-C5H3N-C5H4N)Ru(PPh3)2Cl][PF6] (4) and [(HO-C5H3N-CH2-C5H3N-C5H4N)Ru(PPh3)2OH][PF6] (5) bearing an unsymmetrical pincer NNN ligand with a 2-hydroxypyridylmethylene fragment, and [(CH3O-C5H3N-CH2-C5H3N-C5H4N)2Ru][Cl]2 (6) and [(CH3O-C5H3N-CH2-C5H3N-C5H4N)2Ru][PF6]2 (7) containing 2-methoxypyridylmethylene

  合成了五种钌（II）配合物，包括（HO-C 5 H 3 N-CH 2 -C 5 H 3 N-C 5 H 4 N）Ru（PPh 3）Cl 2（3），[（HO-C 5 H 3 N-CH 2 -C 5 H 3 N-C 5 H 4 N）Ru（PPh 3）2 Cl] [PF 6 ]（4）和[（HO-C 5 H 3 N-CH 2 -C 5 H3 N-C 5 H 4 N）Ru（PPh 3） 2 OH] [PF 6 ]（ 5）带有一个不对称的NNN配体，带有2-羟基吡啶基亚甲基片段，和[（CH 3 O-C 5 H 3 N-CH 2 -C 5 H 3 N-C 5 H 4 N） 2 Ru] [Cl] 2（ 6）和[（CH 3 O-C 5 H 3 N-CH 2 -C 5 H 3 N-C 5 H 4N）2的Ru] [PF 6 ] 2（7）含有2- methoxypyridylmethylene部分。4在室温下与H
• Highly Regio‐ and Stereoselective Hydrosilylation of Alkynes Catalyzed by Tridentate Cobalt Complexes
  作者：Degong Kong、Bowen Hu、Dafa Chen

  DOI：10.1002/asia.201900577

  日期：2019.8

  Several cobalt complexes bearing tridentate (NNN) ligands were synthesized and served as precatalysts for alkyne hydrosilylation with Ph2SiH2. For terminal alkynes, the catalyst L2 b‐CoCl2 was selected, and resulted in the corresponding α‐vinylsilanes with high (Markovnikov) regioselectivity and extensive functional‐group tolerance. For internal diaryl alkynes, the catalyst L2 c‐CoCl2 exhibited the

  合成了带有三齿（NNN）配体的几种钴配合物，并用作用Ph 2 SiH 2进行炔烃氢化硅烷化的预催化剂。对于末端炔烃，选择了催化剂L2 b-CoCl 2，得到的相应的α-乙烯基硅烷具有较高的（马尔可夫尼科夫）区域选择性和广泛的官能团耐受性。对于内部二芳基炔烃，催化剂L2 c-CoCl 2表现出最好的活性，并且在温和的条件下通过合成加成反应提供了E选择性乙烯基硅烷。
• Unexpected Ni(ii) and Cu(ii) polynuclear assemblies—a balance between ligand and metal ion coordination preferences
  作者：Kontantin V. Shuvaev、Santokh S. Tandon、Louise N. Dawe、Laurence K. Thompson

  DOI：10.1039/c0cc00150c

  日期：——

  Polytopic ligand design involves matching the coordination pocket composition with the metal ion coordination ‘algorithm’, but despite targeting [4 × 4] grids as the final outcome, metal ion preferences and ligand control can lead to widely varying complexes in the self-assembly process with Ni(II) and Cu(II).

  多位配体设计涉及配位口袋成分与金属离子配位 "算法 "的匹配，尽管最终结果以[4 Ã 4]网格为目标，但金属离子的偏好和配体控制可能会导致镍（II）和铜（II）在自组装过程中产生千差万别的配合物。