3,8-bis(4-bromo-2'-pyridyl)-4,7-phenanthroline | 915283-61-3

• 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: 3,8-bis(4-bromo-2'-pyridyl)-4,7-phenanthroline
• 英文别名: 3,8-Bis(5-bromopyridin-2-YL)-4,7-phenanthroline；3,8-bis(5-bromopyridin-2-yl)-4,7-phenanthroline
• CAS: 915283-61-3
• 化学式: C₂₂H₁₂Br₂N₄
• 分子量: 492.172
• InChiKey: MWVKBKCRGRLZCY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  28
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,8-bis(4-bromo-2'-pyridyl)-4,7-phenanthroline 、 4-(三甲基硅烷)苯硼酸 在 potassium phosphate 、 四(三苯基膦)钯 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 28.0h， 以66%的产率得到3,8-bis(4-(4-methoxyphenyl)-2'-pyridyl)-4,7-phenanthroline
  参考文献：
  名称：

  Cyclic [2]Pseudorotaxane Tetramers Consisting of Two Rigid Rods Threaded through Two Bis-Macrocycles: Copper(I)-Templated Synthesis and X-ray Structure Studies

  摘要：

  Variously substituted coordinating rigid rods have been synthesized which incorporate a central 4,7-phenanthroline nucleus attached to two 2-pyridyl groups via its 3 and 8 positions, so as to yield bis-bidentate chelates, the two-coordinating axes of the chelates being parallel to one another. Regardless of the nature of the substituents borne by the rods, the copper(I)-induced threading reaction of two such rods through the rings of two bis-macrocycles affords in a quantitative yield the 4-copper(I) threaded assembly. The [2]pseudorotaxane tetramers thus obtained have been fully characterized in solution and, for one of them, an X-ray structure could be obtained, confirming the threaded nature of the complex and providing important structural information.

  DOI：

  10.1021/ja801924y
• 作为产物：
  描述：

  5-bromo-2-(trimethylstannyl)pyridine 、 3,8-dibromo-4,7-phenanthroline 在 四(三苯基膦)钯 作用下， 以 甲苯 为溶剂， 反应 62.0h， 以87%的产率得到3,8-bis(4-bromo-2'-pyridyl)-4,7-phenanthroline
  参考文献：
  名称：

  Copper(i)-induced threading of two bis-macrocycles on two rods: a cyclic [4]rotaxane

  摘要：

  以铜（I）为模板，通过将两个双配位点棒穿过两个双大环，在室温下定量合成了环状假轮烷四聚体。

  DOI：

  10.1039/b601703g

文献信息

• [3]Rotaxanes and [3]pseudorotaxanes with a rigid two-bidentate chelate axle threaded through two coordinating rings
  作者：Jean-Paul Collin、Jean-Pierre Sauvage、Yann Trolez、Kari Rissanen

  DOI：10.1039/b9nj00278b

  日期：——

  New [3]rotaxanes and [3]pseudorotaxanes have been synthesised using the “gathering and threading” effect of copper(I). By using click chemistry as the “stoppering” reaction, a good yield of the [3]rotaxane was obtained, either as a dicopper complex or as a metal-free compound after demetallation. The axle contains a central rigid aromatic block incorporating two bidentate chelates, and the threaded macrocycles are 30-membered rings. A model dicopper(I) [3]pseudorotaxane whose axle was end-functionalised by triisopropylsilyl groups could be crystallised and studied by X-ray diffraction. A particularly attractive structure was obtained showing a “slanted” geometry for the two rings and the axle, the two 1,10-phenanthroline units of the rings being almost parallel to one another but their respective mean planes being more than 7 Å apart.

  新的[3]轮烷和[3]假轮烷已通过铜(I)的“聚集和穿线”效应合成。使用点击化学作为“塞子”反应，获得了高产率的[3]轮烷，无论作为二铜配合物还是在脱金属后作为无金属化合物。轴包含一个中心刚性芳香块，结合了两个双齿螯合剂，而穿过的宏环是30元环。一个轴端功能化为三异丙基硅基的二铜(I)[3]假轮烷模型可以结晶并通过X射线衍射研究。获得了一个特别吸引人的结构，显示出两个环和轴的“倾斜”几何形状，两个1,10-菲咯啉单元几乎平行，但它们各自的平均平面相距超过7 Å。
• Copper(i)-induced threading of two bis-macrocycles on two rods: a cyclic [4]rotaxane
  作者：Jean-Paul Collin、Julien Frey、Val?rie Heitz、Efstathia Sakellariou、Jean-Pierre Sauvage、Christian Tock

  DOI：10.1039/b601703g

  日期：——

  A cyclic pseudo-rotaxane tetramer has been synthesised quantitatively at room temperature by threading two two-coordination site rods through two bis-macrocycles in the presence of copper(I) as a template.

  以铜（I）为模板，通过将两个双配位点棒穿过两个双大环，在室温下定量合成了环状假轮烷四聚体。
• Synthesis of [5]Rotaxanes Containing Bi- and Tridentate Coordination Sites in the Axis
  作者：Jean-Paul Collin、Stéphanie Durot、Michel Keller、Jean-Pierre Sauvage、Yann Trolez、Mario Cetina、Kari Rissanen

  DOI：10.1002/chem.201002220

  日期：2011.1.17

  chelating groups), thus inhibiting potential detrimental side reactions during the copper‐catalyzed stoppering reaction. Since the external fragments and the central core of the system contain tri‐ and bidentate chelating units, respectively, the axle of the final [5]rotaxane incorporates two types of coordinating units: two external terpy groups (terpy: 2,2′:6′,2′′‐terpyridine) and two central bidentate

  线性[5]轮烷的一个新例子是使用传统的“聚集和穿线”方法合成的，但是基于一个不寻常的车轴，该车轴包含一个在4,7-菲咯啉核上构建的对称双（双齿）螯合片段。终止反应特别值得注意，因为使用了两个半封闭的铜络合的[2]假轮烷（即[2] semirotaxanes），从而生成了所需的[5]轮烷，而不是使用琐碎的笨拙的塞子作为封闭基团的前体。产量高。该方法的效率取决于使用“喀哒”化学反应及其非常温和的条件，并依赖于过渡金属（铜（I））对要相互连接的片段中存在的各种配位基团（叔丁基）的保护。和双齿螯合组），从而抑制了铜催化的塞化反应中潜在的有害副反应。由于系统的外部片段和中央核心分别包含三齿和双齿螯合单元，因此最终的[5]轮烷的轴包含两种类型的协调单元：两个外部萜基基团（萜基：2,2'：6 '，2''-三吡啶）和两个中央双齿配体。这种情况使系统可以整理两个不同的金属中心，并将它们定位在事先定义好的位置
• Cyclic [2]Pseudorotaxane Tetramers Consisting of Two Rigid Rods Threaded through Two Bis-Macrocycles: Copper(I)-Templated Synthesis and X-ray Structure Studies
  作者：Julien Frey、Christian Tock、Jean-Paul Collin、Valérie Heitz、Jean-Pierre Sauvage、Kari Rissanen

  DOI：10.1021/ja801924y

  日期：2008.8.1

  Variously substituted coordinating rigid rods have been synthesized which incorporate a central 4,7-phenanthroline nucleus attached to two 2-pyridyl groups via its 3 and 8 positions, so as to yield bis-bidentate chelates, the two-coordinating axes of the chelates being parallel to one another. Regardless of the nature of the substituents borne by the rods, the copper(I)-induced threading reaction of two such rods through the rings of two bis-macrocycles affords in a quantitative yield the 4-copper(I) threaded assembly. The [2]pseudorotaxane tetramers thus obtained have been fully characterized in solution and, for one of them, an X-ray structure could be obtained, confirming the threaded nature of the complex and providing important structural information.