2,2'-dichloro-5,5'dibromo-4,4'-bipyridine | 1227402-54-1

• 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'-dichloro-5,5'dibromo-4,4'-bipyridine
• 英文别名: 5,5'-dibromo-2,2'-dichloro-4,4'-bipyridine；5,5'-dibromo-2,2'-dichloro-[4,4']bipyridinyl；5-bromo-4-(5-bromo-2-chloropyridin-4-yl)-2-chloropyridine
• CAS: 1227402-54-1
• 化学式: C₁₀H₄Br₂Cl₂N₂
• 分子量: 382.869
• InChiKey: XOVNLSUYCAEACP-UHFFFAOYSA-N

物化性质

• 沸点：
  379.7±37.0 °C(Predicted)
• 密度：
  1.939±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 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

安全信息

• 危险性防范说明：
  P264,P280,P302+P352,P337+P313,P305+P351+P338,P362+P364,P332+P313
• 危险性描述：
  H315,H319

反应信息

• 作为反应物：
  描述：

  2,2'-dichloro-5,5'dibromo-4,4'-bipyridine 在 正丁基锂 、 碘 作用下， 以 四氢呋喃 为溶剂， 反应 0.42h， 以70%的产率得到2,2'-dichloro-5,5'-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：

  5-溴-2-氯吡啶 在 lithium diisopropyl amide 、 碘 作用下， 以 四氢呋喃 为溶剂， 反应 2.17h， 以65%的产率得到2,2'-dichloro-5,5'dibromo-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

• Double N-arylation reaction of polyhalogenated 4,4’-bipyridines. Expedious synthesis of functionalized 2,7-diazacarbazoles
  作者：Mohamed Abboud、Emmanuel Aubert、Victor Mamane

  DOI：10.3762/bjoc.8.26

  日期：——

  Unusual 2,7-diazacarbazoles were prepared in one step from readily available tetra-halogenated 4,4’-bipyridines by using a double N-arylation reaction in the presence of the Pd–XPhos catalyst system. Moderate to good yields were obtained in this site-selective Buchwald–Hartwig double amination. The functionalization of these tricyclic derivatives was performed by using Pd-catalyzed cross-coupling reactions such as the Stille and Suzuki couplings. Two compounds were analyzed by X-ray diffraction and show π–π stacking involving the diazacarbazole moieties and the phenyl rings of functionalized groups.

  使用Pd-XPhos催化系统，在双N芳基化反应的存在下，从易得的四卤代4,4'-联吡啶中一步制备了不寻常的2,7-二氮杂咯。在这种位选择性的Buchwald-Hartwig双胺化反应中获得了中等至良好的产率。通过使用Pd催化的交叉偶联反应，如Stille和Suzuki偶联，对这些三环衍生物进行了官能化。通过X射线衍射分析了两种化合物，并显示了涉及二氮杂咯基团和官能化基团的苯环之间的π-π堆积。
• Lithiation of Prochiral 2,2′-Dichloro-5,5′-dibromo-4,4′-bipyridine as a Tool for the Synthesis of Chiral Polyhalogenated 4,4′-Bipyridines
  作者：Victor Mamane、Emmanuel Aubert、Paola Peluso、Sergio Cossu

  DOI：10.1021/jo401255q

  日期：2013.8.2

  achiral tetrahalogenated 4,4′-bipyridine 1 with alkyllithiums was investigated. n-BuLi was found to induce either the chlorine-directed deprotolithiation reaction alone or with a concomitant halogen–lithium exchange furnishing after iodine trapping chiral 4,4′-bipyridines 2 and 6, respectively. The role of n-BuLi in the deprotolithiation process of 1 was elucidated on the basis of isolated secondary derivatives

  研究了非手性四卤代4,4'-联吡啶1与烷基锂的锂化。在碘分别捕获手性4,4'-联吡啶2和6后，发现n -BuLi单独诱导氯定向脱锂反应或伴随卤素-锂交换。基于分离的二级衍生物，阐明了n -BuLi在1的去锂化过程中的作用。去原锂化后，锂化的物种可能被不同的亲电试剂（例如MeI，TMCCl，MeSSMe，R 3 SnCl（R = Me或n -Bu）和PPh 2）捕获。Cl。此外，4,4'-联吡啶2经历了交叉偶联反应（铃木和Sonogashira），选择性地发生在碳碘键上。通过手性HPLC（高效液相色谱）分离该新的对映异构体4,4'-联吡啶家族的所有化合物，并使用反常色散通过XRD（X射线衍射）确定获得的对映异构体的绝对构型。
• 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.
• Chiral Hexahalogenated 4,4′-Bipyridines
  作者：V. Mamane、P. Peluso、E. Aubert、S. Cossu、P. Pale

  DOI：10.1021/acs.joc.6b00413

  日期：2016.6.3

  Finkelstein reaction (Buchwald procedure) performed on 2,2′-dibromo derivatives. Selected compounds of this new family of atropisomeric 4,4′-bipyridines were enantioseparated by high performance liquid chromatography on chiral stationary phases, and the absolute configurations of the separated enantiomers were assigned by using X-ray diffraction analysis. The latter revealed that various halogen bond

  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。