1,2-二溴二茂铁 | 238413-86-0

• 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: 1,2-二溴二茂铁
• 英文名称: 1,2-dibromoferrocene
• 英文别名: cyclopenta-1,3-diene;1,5-dibromocyclopenta-1,3-diene;iron(2+)
• CAS: 238413-86-0
• 化学式: C₁₀H₈Br₂Fe
• 分子量: 343.829
• InChiKey: KHWAWVJKMMPWNX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  1,2-二溴二茂铁 在 正丁基锂 、 碘 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.5h， 以98%的产率得到2-bromo-1-iodoferrocene
  参考文献：
  名称：

  1,2-二取代二茂铁的改进合成

  摘要：

  1,2-二取代的二茂铁，特别是1,2-二卤代二茂铁，是重要的原料。在此，我们描述了 1,2-二取代二茂铁（例如 1,2-二溴和 1,2-二碘二茂铁以及 1-溴-2-碘二茂铁和 1-溴-2-氟二茂铁）的显着改进的高产合成. DFT 计算表明，1,2-二卤二茂铁的最高占据分子轨道 (HOMO) 能量差异不大；然而，它们的最低未占分子轨道 (LUMO) 能量——因此是 HOMO/LUMO 间隙——与卤素电负性的总和相关。此外，还提出了一种相当敏感的 2-氨基二茂铁羧酸（邻氨基苯甲酸的二茂铁类似物）的合成，它从二茂铁-1,2-二羧酸开始。然而，2-氨基二茂铁羧酸迅速分解，因此无法正确表征。二茂铁-1,2-二羧酸酐用作初步光化学脱羰/脱羧实验的起始材料，当在[D8]甲苯中进行时产生1,2-二氘代二茂铁。

  DOI：

  10.1002/ejic.201600766
• 作为产物：
  描述：

  溴代二茂铁 在 2,2,6,6-tetramethylpiperidinyl-lithium 、 溴 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 3.75h， 以50%的产率得到1,2-二溴二茂铁
  参考文献：
  名称：

  氰化反应合成1,2-二氰二茂铁

  摘要：

  我们报告了制备 1,2-二氰基二茂铁的两种合成途径，以寻找可用于合成含茂金属氮杂卟啉以及催化的新的二腈基前体。这两个过程都包括氰化反应作为关键步骤。氰基二茂铁的镁化，然后与亲电的甲苯磺酰氰反应，只需两步从二茂铁合成目标化合物。此外，1,2-二氰二茂铁可以通过三步程序制备，这意味着使用 Zn(CN) 对 1,2-二溴二茂铁进行双重氰化2, 在双相介质和大体积的存在下吨-BuXPhos-Pd-G3。

  DOI：

  10.1142/s1088424619501852

文献信息

• 1,2,3,4,5-Pentabromoferrocene and related compounds: A simple synthesis of useful precursors
  作者：Ian R. Butler

  DOI：10.1016/j.inoche.2008.01.015

  日期：2008.5

  Abstract Key bromoferrocenes have been prepared using a simple, yet effective, lithiation and quench methodology. These include 1,2,3-tribromoferrocene and 1,2,3,4,5-pentabromoferrocene. The synthetic method reported can be applied to make a broad range of bromoferrocenes.

  摘要 使用简单而有效的锂化和淬火方法制备了关键的溴二茂铁。这些包括1,2,3-三溴二茂铁和1,2,3,4,5-五溴二茂铁。报道的合成方法可用于制造广泛的溴二茂铁。
• Coordination chemistry of perhalogenated cyclopentadienes and alkynes. XXVIII new high-yield synthesis of monobromoferrocene and simplified procedure for the synthesis of pentabromoferrocene. Molecular structures of 1,2,3-tribromoferrocene and 1,2,3,4,5-pentabromoferrocene
  作者：Karlheinz Sünkel、Stefanie Bernhartzeder

  DOI：10.1016/j.jorganchem.2010.12.028

  日期：2011.4

  Monobromoferrocene (1) was obtained in 95% yield from ferrocene via lithiation with tert-BuLi/KO-tert-Bu and bromination with dibromotetrachloroethane. Starting from 1 mixtures of 1,2-dibromoferrocene (2) and apparently unreacted 1 (ranging from 80:20 to 50:50, depending on the reaction conditions) can be obtained via a lithiation- zincation- bromination sequence. These mixtures can be transferred

  通过用叔-BuLi / KO-叔-Bu锂化并用二溴四氯乙烷溴化，从二茂铁中以95％的产率获得单溴二茂铁（1）。从开始1个1,2- dibromoferrocene（的混合物2）和未反应的明显1（范围从80:20至50:50，这取决于反应条件）可以得到通过lithiation- zincation-溴化序列。可将这些混合物与十倍过量的四甲基哌啶锂直接转移，然后用1,1,2,2-四溴乙烷溴化为五溴二茂铁（3），从二茂铁开始，总收率为36％。3的分子结构通过X射线衍射确定了1,2,3-三溴二茂铁（4）中的α和β 。
• Halide-Mediated<i>Ortho</i>-Deprotonation Reactions Applied to the Synthesis of 1,2- and 1,3-Disubstituted Ferrocene Derivatives
  作者：Afrooz Zirakzadeh、Alexander Herlein、Manuela A. Groß、Kurt Mereiter、Yaping Wang、Walter Weissensteiner

  DOI：10.1021/acs.organomet.5b00464

  日期：2015.8.10

  The ortho-deprotonation of halide-substituted ferrocenes by treatment with lithium tetramethylpiperidide (LiTMP) has been investigated. Iodo-, bromo-, and chloro-substituted ferrocenes were easily deprotonated adjacent to the halide substituents. The synthetic applicability of this reaction was, however, limited by the fact that, depending on the temperature and the degree of halide substitution, scrambling of both iodo and bromo substituents at the ferrocene core took place. Iodoferrocenes could not be transformed selectively into ortho-substituted iodoferrocenes since, in the presence of LiTMP, the iodo substituents scrambled efficiently even at -78 degrees C, and this process had occurred before electrophiles had been added. Bromoferrocene and certain monobromo-substituted derivatives, however, could be efficiently ortho-deprotonated at low temperature and reacted with a number of electrophiles to afford 1,2- and 1,2,3-substituted ferrocene derivatives. For example, 2-bromo-1-iodoferrocene was synthesized by ortho-deprotonation of bromoferrocene and reaction with the electrophiles diiodoethane and diiodotetrafluoroethane, respectively. In this and related cases the iodide scrambling process and further product deprotonation due to the excess LiTMP could be suppressed efficiently by running the reaction at low temperature and in inverse mode. In contrast to the low-temperature process, at room temperature bromo substituents in bromoferrocenes scrambled in the presence of LiTMP. Chloro- and 1,2-dichloroferrocene could be ortho-deprotonated selectively, but in neither case was scrambling of a chloro substituent observed. As a further application of this ortho-deprotonation reaction, a route for the synthesis of 1,3-disubstituted ferrocenes was developed. 1,3-Diiodoferrocene was accessible from bromoferrocene in four steps. On a multigram scale an overall yield of 41% was achieved. 1,3-Diiodoferrocene was further transformed into symmetrically 1,3-disubstituted ferrocenes (1,3-R(2)Fc; R = CHO, COOEt, CN, CH=CH2).
• The conversion of 1,1′-dibromoferrocene to 1,2-dibromoferrocene: The ferrocene-chemist’s dream reaction
  作者：Ian R. Butler

  DOI：10.1016/j.inoche.2007.09.020

  日期：2008.1

  The conversion of 1,1'-dibromoferrocene to a range of 2-substituted bromoferrocenes is described. The products are useful in the preparation of a wide number of 1,2-disubstituted ferrocenes. This includes the preparation of 1,2-dibromoferrocene and 2-(diisopropylphosphino)bromoferrocene in what is a clean and simple synthesis. The synthesis may be carried out on a large scale and for the first time produces multigram quantities of these important precursor compounds. In addition the synthetic procedure may be modified to produce a new family of ferrocene-based tris-phosphine ligands such as bis(2-diphenylphosphinoferrocenyl)phenylphosphine. (c) 2007 Elsevier B.V. All rights reserved.