6,6''-Cl2-2,2':6',2''-terpyridine | 1361327-25-4

• 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: 6,6''-Cl2-2,2':6',2''-terpyridine
• 英文别名: 6,6''-dichloro-2,2':6',2''-terpyridine；dctpy；2,6-Bis(6-chloropyridin-2-yl)pyridine；2,6-bis(6-chloropyridin-2-yl)pyridine
• CAS: 1361327-25-4
• 化学式: C₁₅H₉Cl₂N₃
• 分子量: 302.163
• InChiKey: QNEVWLHKZQMPRM-UHFFFAOYSA-N

物化性质

• 沸点：
  460.5±40.0 °C(Predicted)
• 密度：
  1.351±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  iron(II) tetrafluoroborate hexahydrate 、 6,6''-Cl2-2,2':6',2''-terpyridine 以 1,4-二氧六环 为溶剂， 反应 24.0h， 以51%的产率得到[Fe(6,6''-Cl₂-2,2':6',2''-terpyridine)₂](BF₄)₂
  参考文献：
  名称：

  高应变铁 (II) 多吡啶：利用五重奏歧管延长 MLCT 激发态的寿命

  摘要：

  三联吡啶（6,6"-Cl2-2,2:6',2"-三联吡啶 = dctpy）的 6 和 6" 位置的卤素取代用于产生室温高自旋铁 (II) 络合物 [ Fe(dctpy)2](BF4)2。使用紫外-可见吸收、光谱电化学、瞬态吸收和 TD-DFT 计算，我们提出证据表明五重态金属到配体电荷转移激发态 ((5) MLCT) 可以通过可见光吸收获得，并且热化(5,7) MLCT 的寿命为 16 ps，与 [Fe(bpy)3](2+) 等物种内的 (1,3) MLCT 相比，增加了 > 100 倍。这一结果开辟了一种延长铁 (II) MLCT 寿命的新策略，可用于光氧化还原过程。

  DOI：

  10.1021/jacs.5b13524
• 作为产物：
  描述：

  2,6-二氯吡啶 在 bis(bipyridine)nickel(II) bromide 、 sodium iodide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 3.3h， 以46%的产率得到6,6’-二氯-2,2’-联吡啶
  参考文献：
  名称：

  Electrochemical coupling of mono and dihalopyridines catalyzed by nickel complex in undivided cell

  摘要：

  One step nickel-catalyzed electroreductive homocoupling among 2-bromopicolines and 2-bromopyridine has been investigated by our group in an undivided cell and using zinc or iron as sacrificial anode. In this work, it was developed mono and dihalopyridines coupling to obtain possible products from heterocoupling. A series of reactions were carried out in order to develop a synthetic method for the preparation of unsymmetrical 2,2'-bipyridines and 2,2':6',2 ''-terpyridines. Statistical yields (50%) were observed for 2-bromopyridines/2-bromo-6-methylpyridine heterocoupling. In a preliminary study devoted to terpyridines preparation, good results were obtained for 2,6-dihalopyridines homocoupling, affording 2,6-dichloro-2,2'-bipyridine (46%) and 2,6-dibromo-2,2'-bipyridine (56%), at controlled reaction time. At major reaction time, it was observed that the direct electroreduction of the 2,6'-dihalo-2,2'-bipyridines intermediates and 2,6 ''-dihalo-2,2':6',2 ''-terpyridines products on the cathode surface. A reasonable isolated product yield of 6,6 ''-dimethy1-2,2':6',2 ''-terpyridine (10%) was only observed in the reaction between 2,6-dichloropyridine and 2-bromo-6-methylpyridine (1:2). (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.01.017

文献信息

• Electrochemical coupling of mono and dihalopyridines catalyzed by nickel complex in undivided cell
  作者：Jadson L. Oliveira、Maria J. Silva、Tupolevck Florêncio、Karène Urgin、Stéphane Sengmany、Eric Léonel、Jean-Yves Nédélec、Marcelo Navarro

  DOI：10.1016/j.tet.2012.01.017

  日期：2012.3

  One step nickel-catalyzed electroreductive homocoupling among 2-bromopicolines and 2-bromopyridine has been investigated by our group in an undivided cell and using zinc or iron as sacrificial anode. In this work, it was developed mono and dihalopyridines coupling to obtain possible products from heterocoupling. A series of reactions were carried out in order to develop a synthetic method for the preparation of unsymmetrical 2,2'-bipyridines and 2,2':6',2 ''-terpyridines. Statistical yields (50%) were observed for 2-bromopyridines/2-bromo-6-methylpyridine heterocoupling. In a preliminary study devoted to terpyridines preparation, good results were obtained for 2,6-dihalopyridines homocoupling, affording 2,6-dichloro-2,2'-bipyridine (46%) and 2,6-dibromo-2,2'-bipyridine (56%), at controlled reaction time. At major reaction time, it was observed that the direct electroreduction of the 2,6'-dihalo-2,2'-bipyridines intermediates and 2,6 ''-dihalo-2,2':6',2 ''-terpyridines products on the cathode surface. A reasonable isolated product yield of 6,6 ''-dimethy1-2,2':6',2 ''-terpyridine (10%) was only observed in the reaction between 2,6-dichloropyridine and 2-bromo-6-methylpyridine (1:2). (C) 2012 Elsevier Ltd. All rights reserved.
• Highly Strained Iron(II) Polypyridines: Exploiting the Quintet Manifold To Extend the Lifetime of MLCT Excited States
  作者：Samuel G. Shepard、Steven M. Fatur、Anthony K. Rappé、Niels H. Damrauer

  DOI：10.1021/jacs.5b13524

  日期：2016.3.9

  Halogen substitution at the 6 and 6″ positions of terpyridine (6,6″-Cl2-2,2:6',2″-terpyridine = dctpy) is used to produce a room-temperature high-spin iron(II) complex [Fe(dctpy)2](BF4)2. Using UV-vis absorption, spectroelectrochemistry, transient absorption, and TD-DFT calculations, we present evidence that the quintet metal-to-ligand charge-transfer excited state ((5)MLCT) can be accessed via visible

  三联吡啶（6,6"-Cl2-2,2:6',2"-三联吡啶 = dctpy）的 6 和 6" 位置的卤素取代用于产生室温高自旋铁 (II) 络合物 [ Fe(dctpy)2](BF4)2。使用紫外-可见吸收、光谱电化学、瞬态吸收和 TD-DFT 计算，我们提出证据表明五重态金属到配体电荷转移激发态 ((5) MLCT) 可以通过可见光吸收获得，并且热化(5,7) MLCT 的寿命为 16 ps，与 [Fe(bpy)3](2+) 等物种内的 (1,3) MLCT 相比，增加了 > 100 倍。这一结果开辟了一种延长铁 (II) MLCT 寿命的新策略，可用于光氧化还原过程。