1.2-dichloro ferrocene

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1.2-dichloro ferrocene
• 英文别名: 1,2-dichloroferrocene；[(C₅H₃Cl₂)(C₅H₅)Fe]
• 化学式: C₁₀H₈Cl₂Fe
• 分子量: 254.927
• InChiKey: AOACUUMYCRFOHB-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

• 作为产物：
  描述：

  chloroferrocene 在 2,2,6,6-tetramethylpiperidinyl-lithium 、 六氯乙烷 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 5.75h， 以38%的产率得到1.2-dichloro ferrocene
  参考文献：
  名称：

  Halide-MediatedOrtho-Deprotonation Reactions Applied to the Synthesis of 1,2- and 1,3-Disubstituted Ferrocene Derivatives

  摘要：

  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).

  DOI：

  10.1021/acs.organomet.5b00464

文献信息

• Coordination chemistry of perhalogenated cyclopentadienes and alkynes. Part 30. New high-yield syntheses of monochloroferrocene and 1,2,3,4,5-pentachloroferrocene. Molecular structures of 1,2-dichloroferrocene and 1,2,3-trichloroferrocene
  作者：Stefanie Bernhartzeder、Karlheinz Sünkel

  DOI：10.1016/j.jorganchem.2012.06.016

  日期：2012.10

  Lithiation of ferrocene with KOtBu and tBuLi in tetrahydrofuran at −78 °C, followed by treatment with hexachloroethane gives monochloroferrocene 1 in essentially quantitative yield. Lithiation of 1 with 1.2 equiv. lithium tetramethylpiperidide (LiTMP) in THF and chlorination with C2Cl6 gives 1,2-dichloroferrocene 2 contaminated with 1 and ferrocene. Treatment of this mixture with a tenfold excess of

  在-78°C下在四氢呋喃中用KO t Bu和t BuLi进行二茂铁的锂化，然后用六氯乙烷处理，得到的氯二茂铁1基本定量收率。1与1.2当量的锂化 四甲基哌啶锂（LiTMP）在THF和氯化以C 2氯6给出1,2- dichloroferrocene 2沾染1和二茂铁。用1,2,3,4,5-五氯二茂铁3进行后处理后，用十倍过量的LiTMP和C 2 Cl 6处理该混合物，产率为二茂铁的29％。或者，从1的混合物和2 1,2,3- trichloroferrocene 4和1,2,3,4- tetrachloroferrocene 5可以以逐步的方式用分别为40％和46％，产率来制备。2和4的分子结构已通过X射线衍射确定，并证明了假定的区域化学。
• Evidence for “Halogen‐Dance” and Ring‐Exchange Reactions in Chloro‐methylthio‐ferrocenes
  作者：Tobias Blockhaus、Stefanie Bernhartzeder、Werner Kempinger、Christian Klein‐Heßling、Stefan Weigand、Karlheinz Sünkel

  DOI：10.1002/ejoc.202001032

  日期：2020.11.15

  Br, SMe) and quench with MeSSMe produces complex product mixtures, which include compounds with [C5Cl4(SMe)] ligands or compounds which contained six or more chlorine atoms. The occurrence of such products can only be explained by halogen‐dance and/or cyclopentadienyl ring exchange reactions. Herein, some of the key compounds could be characterized by X‐ray diffraction.

  五氯二茂铁[C 5 Cl 5 ] Fe [C 5 H 4 X]（X = H，Br，SMe）去质子化并用MeSSMe淬灭产生复杂的产物混合物，其中包括具有[C 5 Cl 4（SMe）]配体的化合物或含六个或更多氯原子的化合物。此类产物的出现只能通过卤素跳舞和/或环戊二烯基环交换反应来解释。在此，一些关键化合物可以通过X射线衍射表征。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: B: B-Verb.13, 4.7.2.7, page 226 - 237
  作者：

  DOI：——

  日期：——
• <b>The Carbonylation of Organoboranes. I. The Carbonylation of Trialkylboranes. A Novel Synthesis of Trialkylcarbinols</b>
  作者：Melville E. D. Hillman

  DOI：10.1021/ja00883a020

  日期：1962.12
• 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).

表征谱图