2,2',5,5'-tetrachloro-4,4'-bipyridine

• 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: 2,2',5,5'-tetrachloro-4,4'-bipyridine
• 英文别名: 2,5,2',5'-tetrachloro-[4,4']bipyridinyl；2,5-Dichloro-4-(2,5-dichloropyridin-4-yl)pyridine；2,5-dichloro-4-(2,5-dichloropyridin-4-yl)pyridine
• 化学式: C₁₀H₄Cl₄N₂
• 分子量: 293.967
• InChiKey: BYLBZVFHTZZISM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2',5,5'-tetrachloro-4,4'-bipyridine 在 N-碘代丁二酰亚胺 、 氢溴酸 、 sodium 、 溶剂黄146 、 三氟乙酸 、 三氯氧磷 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 30.5h， 生成 2,2',5,5'-tetrachloro-3,3'-diiodo-4,4'-bipyridine
  参考文献：
  名称：

  手性六氢杂合的4,4'-联吡啶

  摘要：

  描述了通过两种互补方法制备手性六卤代-4,4'-联吡啶的27种异构体。第一种是收敛的，基于LDA诱导的三卤代吡啶的4,4'-二聚，而第二种方法是分歧的，是通过4,4'-联吡啶-2,2'-二酮的区域选择性卤化反应实现的。通过对2，2′-二溴衍生物进行的铜催化的Finkelstein反应（Buchwald方法）引入4，4′-联吡啶的2，2′-位处的碘。通过手性固定相上的高效液相色谱对映这种新的对映异构体4,4'-联吡啶家族的选定化合物，对映体分离，并使用X射线衍射分析确定分离的对映体的绝对构型。

  DOI：

  10.1021/acs.joc.6b00413
• 作为产物：
  描述：

  2,5-二氯吡啶 在 lithium diisopropyl amide 、 碘 作用下， 以 四氢呋喃 为溶剂， 反应 2.17h， 以61%的产率得到2,2',5,5'-tetrachloro-4,4'-bipyridine
  参考文献：
  名称：

  手性六氢杂合的4,4'-联吡啶

  摘要：

  描述了通过两种互补方法制备手性六卤代-4,4'-联吡啶的27种异构体。第一种是收敛的，基于LDA诱导的三卤代吡啶的4,4'-二聚，而第二种方法是分歧的，是通过4,4'-联吡啶-2,2'-二酮的区域选择性卤化反应实现的。通过对2，2′-二溴衍生物进行的铜催化的Finkelstein反应（Buchwald方法）引入4，4′-联吡啶的2，2′-位处的碘。通过手性固定相上的高效液相色谱对映这种新的对映异构体4,4'-联吡啶家族的选定化合物，对映体分离，并使用X射线衍射分析确定分离的对映体的绝对构型。

  DOI：

  10.1021/acs.joc.6b00413

文献信息

• Synthesis of Polyhalogenated 4,4′-Bipyridines via a Simple Dimerization Procedure
  作者：Mohamed Abboud、Victor Mamane、Emmanuel Aubert、Claude Lecomte、Yves Fort

  DOI：10.1021/jo100152e

  日期：2010.5.21

  Polyhalogenated 4,4'-bipyridines were conveniently synthesized in a single step starting from dihalo-pyridines. A mechanism was proposed on the basis of experiments performed with 2-chloro-5-bromopyridine I a. 2-Chloro-4-lithio-5-bromopyridine A1 was produced via ortholithiation of la by using either LDA or t-BuLi bases. When LDA was used, chiller 3a containing two chlorines and two bromine atoms was formed predominantly accompanied by several byproducts whose structure and mechanism of formation are discussed. In the case of t-BuLi, although the major product was 2-chloropyridine 7, a new pyridone product 8 was formed that is probably the result of the dihydropyridine intermediate hydrolysis. The dimerization procedure involving LDA was employed to prepare a large number of halogenated 4,4'-bipyridines in moderate to good yields. In some specific cases, halogenated 3,4' and 2,4'-bipyridines were obtained in lower yields and their structures were unambiguously assigned by X-ray diffraction analysis.
• Deprotonation of chloropyridines using lithium magnesates
  作者：Haçan Awad、Florence Mongin、François Trécourt、Guy Quéguiner、Francis Marsais

  DOI：10.1016/j.tetlet.2004.08.151

  日期：2004.10

  4-Chloropyridine was deprotonated on treatment with 1/3 equiv of the highly coordinated magnesate Bu-3(TMP)MgLi2 in THF at -10degreesC, as evidenced by trapping with I-2. The use of Bu(TMP)(2)MgLi in Et2O allowed the reaction of 2-chloropyridine, giving the 3-functionalized derivative as the main product. Mixtures of 3- and 4-functionalized derivatives were obtained when 2,6-dichloropyridine was involved in the reaction. Performing the reaction on 3-chloropyridine with lithium magnesates in THF, either the 4,4'-dimer or the 4-iodo derivative was formed after quenching by I-2, the former using 1/3equiv of Bu-2(TMP)MgLi and the latter using 1 equiv of (TMP)(3)MgLi. Similar results were observed with 3,5-dichloropyridine, 2,5-dichloropyridine and 3-chloro-2-fluoropyridine. 1,2-Migration of the lithium arylmagnesate formed by deprotonation was proposed to justify the dimers formation. (C) 2004 Elsevier Ltd. All rights reserved.