6,6''-二(溴甲基)-[2,2':6',2''-三联吡啶]-4'-羧酸乙酯 | 372520-85-9

• 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: 6,6''-二(溴甲基)-[2,2':6',2''-三联吡啶]-4'-羧酸乙酯
• 英文名称: ethyl 6,6''-bis-(bromomethyl)-2,2':6',2''-terpyridine-4'-carboxylate
• 英文别名: ethyl 6,6'-dibromomethyl-4'-(2,2':6',2''-terpyridine)carboxylate；Ethyl 2,6-bis[6-(bromomethyl)pyridin-2-yl]pyridine-4-carboxylate
• CAS: 372520-85-9
• 化学式: C₂₀H₁₇Br₂N₃O₂
• 分子量: 491.182
• InChiKey: DRSSOZTTWXYVKX-UHFFFAOYSA-N

物化性质

• 沸点：
  569.7±50.0 °C(Predicted)
• 密度：
  1.568±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  65
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  6,6''-二(溴甲基)-[2,2':6',2''-三联吡啶]-4'-羧酸乙酯 在 lithium aluminium tetrahydride 、 三溴化磷 、 sodium hydride 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 5.5h， 生成 tetraethyl (4′-bromomethyl-2,2′:6′,2′-terpyridine-6,6′-diyl)bis(methylenenitrilo)tetrakis(acetate)
  参考文献：
  名称：

  A Ratiometric Luminescence Probe for Highly Reactive Oxygen Species Based on Lanthanide Complexes

  摘要：

  Reactive oxygen species (ROS) are important mediators in a variety of pathological events, but the oxidative stress owing to excessive generation of ROS is implicated in many human diseases. In this work, we designed and synthesized a novel dual-functional chelating ligand, [4'-(p-aminophenoxy)methylene-2,2':6',2 ''-terpyridine-6,6 ''-diyl]bis(tnethylenenitrilo)tetrakis(acetic acid) (AMTTA), that can strongly coordinate with both Eu3+ and Tb3+ in aqueous solutions for the recognition and time-gated luminescence detection of highly ROS (hROS), hydroxyl radical ((OH)-O-center dot), and hypochlorite (ClO-). The complexes AMTTA-Ln(3+) (Ln = Eu and Tb) are almost nonluminescent because of the photoinduced electron transfer from the electron-rich aminophenyl group to the terpyridine-Ln(3+) moiety but can rapidly react with hROS to afford highly luminescent complexes (4'-hydroxymethyl-2,2':6',2 ''-terpyridine-6,6 ''-diyl)bis(methylenenitrilo)tetrakis(acetate)- Ln(3+) (HTTA-Ln(3+)). Interestingly, when the AMTTA-Eu3+/Tb3+ mixture (AMTTA/Eu3+/Tb3+ = 2/1/1) was reacted with hROS, the intensity ratio of its Tb3+ emission at 540 nm to its Eu3+ emission at 610 nm, I-540/I-610, showed a ratiometric response toward hROS, and the dose-dependent increase of the ratio displayed a double-exponential correlation to the concentration of hROS. This unique luminescence response allowed the AMTTA-Eu3+/Tb3+ mixture to be used as a ratiometric probe for the time-gated luminescence detection of hROS.

  DOI：

  10.1021/ic202195a
• 作为产物：
  描述：

  2,6-二溴吡啶-4-羧酸乙酯 在 四(三苯基膦)钯 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 作用下， 以 甲苯 、 苯 为溶剂， 反应 51.0h， 生成 6,6''-二(溴甲基)-[2,2':6',2''-三联吡啶]-4'-羧酸乙酯
  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

文献信息

• Direct Access to Terpyridine-Containing Polyazamacrocycles as Photosensitizing Ligands for Eu(III) Luminescence in Aqueous Media
  作者：Chantal Galaup、Jean-Marc Couchet、Sébastien Bedel、Pierre Tisnès、Claude Picard

  DOI：10.1021/jo0480242

  日期：2005.3.1

  The photophysical properties of the Eu(III) complexes derived from these ligands were examined in aqueous solutions. Their luminescence lifetimes (τ ≈ 1 ms) and quantum yields (13% < Φ < 18%) on one hand, their high kinetic inertness on the other hand, and the presence of additional functionality allowing their covalent conjugation to biomolecules seriously nominate these complexes as very promising

  描述了包含功能化的2,2'：6'，2''-叔吡啶部分作为环状骨架一部分和三个乙酸酯侧链的新的18元六氮杂大环的合成。报道的合成方法是基于控制大环化步骤的有效金属模板离子效应的使用。该程序与大环结构中存在的某些官能团兼容。在水溶液中检查了衍生自这些配体的Eu（III）配合物的光物理性质。它们的发光寿命（τ≈1 ms）和量子产率（13％<Φ<18％）一方面，它们的高动力学惰性，
• Synthesis of bisfunctionalized-oligopyridines bearing an ester group
  作者：Gilles Ulrich、Sébastien Bedel、Claude Picard、Pierre Tisnès

  DOI：10.1016/s0040-4039(01)01195-9

  日期：2001.8

  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.