1-(2-bromoethyl)-3-(2,4,6-trimethylphenyl)imidazolium bromide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1-(2-bromoethyl)-3-(2,4,6-trimethylphenyl)imidazolium bromide
• 英文别名: 1-(2-Bromoethyl)-3-(2,4,6-trimethylphenyl)imidazol-1-ium;bromide
• 化学式: Br*C₁₄H₁₈BrN₂
• 分子量: 374.118
• InChiKey: XKYXGFGWFRPUQL-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.09
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  8.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(2-bromoethyl)-3-(2,4,6-trimethylphenyl)imidazolium bromide 在 sodium hydroxide 作用下， 以 水 、 乙腈 为溶剂， 反应 1.0h， 生成 C₁₄H₁₇N₂S⁽¹⁺⁾*CNS^(1-)
  参考文献：
  名称：

  Fused azole-thiazolines via one-pot cyclization of functionalized N-heterocyclic carbene precursors

  摘要：

  通过一种新的一锅法，可以从廉价的起始材料中获得各种双/三环唑-噻唑烯。

  DOI：

  10.1039/c9ob02548k
• 作为产物：
  描述：

  1-(2,4,6-三甲基苯基)-咪唑 在 三溴化磷 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 33.0h， 生成 1-(2-bromoethyl)-3-(2,4,6-trimethylphenyl)imidazolium bromide
  参考文献：
  名称：

  Nickel(II) complexes with bifunctional phosphine–imidazolium ligands and their catalytic activity in the Kumada–Corriu coupling reaction

  摘要：

  Zwitterionic Ni(II) complexes of type NiX3(NCN+), (NCN+ = 1-(2-diphenylphosphinoethyl)-3-(2,4,6-trimethylphenyl)imidazolium and X = Cl, 6; Br, 7), have been prepared by addition of NCN+ bromide (1a) or tetrafluoroborate (1b) to NiX2L, and characterised by X-ray crystallography. They have been used as catalytic precursors in the Kumada-Corriu coupling reaction between phenylmagnesium chloride and 4-chloroanisole, yielding high catalytic activities. Stoechiometric deprotonation investigations did not provide clear evidence for the formation of coordinated carbene species. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.09.010

文献信息

• CSC-pincer versus pseudo-pincer complexes of palladium(ii): a comparative study on complexation and catalytic activities of NHC complexes
  作者：Dan Yuan、Haoyun Tang、Linfei Xiao、Han Vinh Huynh

  DOI：10.1039/c1dt10269a

  日期：——

  Three thioether bridged diimidazolium dibromides with different steric and electronic properties have been synthesized as precursors to carbene-based CSC pincer ligands. Palladation afforded CSC Pd(II) pincer complexes for bulky and electron rich ligand systems, whereas the least donating ligand led to the formation of a pseudo-pincer complex. All complexes have been fully characterized by multinuclei NMR spectroscopies, ESI mass spectrometry and X-ray diffraction analysis. The catalytic activities of pincer versus pseudo-pincer complexes have been compared in the intermolecular hydroamination of alkynes with anilines as well.

  三种具有不同立体和电子性质的三硫醚桥连二咪唑鎓二溴化物已被合成作为基于卡宾的CSC钳形配体的前体。对这些配体进行钯化得到CSC Pd(II)钳形配合物，适用于空间位阻大且电子富集的配体系统，而电子捐赠能力最弱的配体则导致了伪钳形配合物的形成。所有配合物都通过多核NMR光谱、ESI质谱和X射线衍射分析得到了充分表征。此外，钳形配合物与伪钳形配合物的催化活性也在炔烃与苯胺的分子间氢胺化反应中进行了比较。
• Highly Efficient Heck Reactions of Aryl Bromides with <i>n</i>-Butyl Acrylate Mediated by a Palladium/Phosphine−Imidazolium Salt System
  作者：Chuluo Yang、Hon Man Lee、Steven P. Nolan

  DOI：10.1021/ol015827s

  日期：2001.5.1

  [reaction: see text] A new phosphine-imidazolium salt, L.HBr (1, L = (1-ethylenediphenylphosphino-3-(mesityl))imidazol-2-ylidene), has been prepared. A combination of 0.5 mol % of Pd(dba)(2) and 0.5 mol % of L.HBr in the presence of 2 equiv of Cs(2)CO(3) as base has proven to be highly efficient in the Heck coupling reactions of aryl bromides (from electron-deficient to electron-rich aryl bromides)

  [反应：见正文]制备了一种新的膦-咪唑鎓盐L.HBr（1，L =（1-乙烯二苯基膦基-3-（甲磺酰基））咪唑-2-亚甲基）。在2当量Cs（2）CO（3）作为碱的情况下，0.5 mol％的Pd（dba）（2）和0.5 mol％的L.HBr的组合已被证明在Heck偶联反应中非常有效丙烯酸正丁酯制备芳基溴化物（从缺电子到富电子的芳基溴化物）。
• Nickel(II), Palladium(II) and Rhodium(I) Complexes of New NHC‐Thioether Ligands: Efficient Ketone Hydrosilylation Catalysis by a Cationic Rh Complex
  作者：Joffrey Wolf、Agnès Labande、Jean‐Claude Daran、Rinaldo Poli

  DOI：10.1002/ejic.200700670

  日期：2007.11

  for complexation studies on various transition metals (NiII, PdII and RhI). Sulfur does not coordinate the nickel centre, whereas the two functional groups bind the palladium centre to form a dinuclear compound. Cationic rhodium(I) complexes have also been prepared and preliminary catalytic tests show that they have good activity for the hydrosilylation of ketones. (© Wiley-VCH Verlag GmbH & Co. KGaA

  五个新的双功能咪唑鎓-硫醚配体，通式为 RS(CH2)n(咪唑鎓)+ArBr–（n = 2 或 3，R = Et 或 tBu，Ar = 2,4,6-三甲基苯基或 2,6-二异丙基苯基）已通过一般方法以良好的总产率合成，并用作 N-杂环卡宾前体，用于各种过渡金属（NiII、PdII 和 RhI）的络合研究。硫不与镍中心配位，而两个官能团与钯中心结合形成双核化合物。还制备了阳离子铑（I）配合物，初步催化试验表明它们对酮的氢化硅烷化具有良好的活性。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Reactivity of Phosphane–Imidazolium Salts Towards [Ir(COD)Cl] ₂ : Preparation of New Hydridoiridium(III) Complexes Bearing Abnormal Carbenes
  作者：Joffrey Wolf、Agnès Labande、Jean‐Claude Daran、Rinaldo Poli

  DOI：10.1002/ejic.200800270

  日期：2008.7

  The unusual reactivity of chelating phosphane–imidazolium salts MesImEtPPh2+Br–, DIPP-ImEtPPh2+Br–, and MesImEtPPh2+BF4– towards the low-oxidation-state iridium complex [Ir(COD)(μ-Cl)]2 was studied. In the absence of a base, the C–H insertion at the C5 position of the imidazolium ring was the only reaction that occurred, with no normal NHC observed, leading to hydridoiridium(III) complexes. This reactivity

  研究了螯合磷烷-咪唑鎓盐 MesImEtPPh2+Br–、DIPP-ImEtPPh2+Br– 和 MesImEtPPh2+BF4– 对低氧化态铱络合物 [Ir(COD)(μ-Cl)]2 的异常反应性。在没有碱基的情况下，咪唑环 C5 位置的 C-H 插入是唯一发生的反应，没有观察到正常的 NHC，导致形成氢化铱 (III) 络合物。这种反应性与咪唑鎓抗衡阴离子的性质和芳基的取代模式无关。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Syntheses and characterizations of thiolato-functionalized N-heterocyclic carbene Pd(ii) complexes with normal and mesoionic binding modes
  作者：Dan Yuan、Han Vinh Huynh

  DOI：10.1039/c1dt10789e

  日期：——

  The thiolato-bridged dimeric Pd(II) NHC complex 1 has been synthesized from the reaction of thioester-functionalized imidazolium salt B and Pd(OAc)2. The isolation of its interesting constitutional isomer 2 bearing both classical C(2)-bound and mesoionic C(4)-bound ligands coordinating to two different metal centers in the same complex allowed for a direct comparison of these isomeric carbenes. Reactivity studies of 1 with NaSCH(CH3)2 and NaBF4 afforded the tetranuclear compound 3 with a [Pd4S4] macrocycle. All complexes have been fully characterized by multinuclei NMR spectroscopies, ESI mass spectrometry and X-ray diffraction analysis.

  硫醇桥联二聚体Pd(II) NHC复合物1是通过硫酯官能化的咪唑鎓盐B和Pd(OAc)2的反应合成的。其有趣的构型异构体2同时带有经典的C(2)键合和介离子C(4)键合配体，与同一复合物中的两个不同的金属中心配位，从而可以直接比较这些异构体羰基。1与NaSCH(CH3)2和NaBF4的反应性研究产生了具有[Pd4S4]大环的四核化合物3。所有复合物均通过多核核磁共振光谱、ESI质谱和X射线衍射分析进行了充分表征。