1-(2,6-diisopropylphenyl)-3-(pyridin-2-ylmethyl)-1H-imidazol-3-ium bromide | 330455-92-0

• 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-(2,6-diisopropylphenyl)-3-(pyridin-2-ylmethyl)-1H-imidazol-3-ium bromide
• 英文别名: 2-[[3-[2,6-Di(propan-2-yl)phenyl]imidazol-1-ium-1-yl]methyl]pyridine;bromide
• CAS: 330455-92-0
• 化学式: Br*C₂₁H₂₆N₃
• 分子量: 400.362
• InChiKey: IMYIJXFXQOTKPE-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.46
• 重原子数：
  25.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  21.7
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-(2,6-diisopropylphenyl)-3-(pyridin-2-ylmethyl)-1H-imidazol-3-ium bromide 在 ionic exchange resin DOVEX 21 KCl 作用下， 生成 1-(2,6-diisopropylphenyl)-3-(pyridin-2-ylmethyl)-1Himidazol-3-ium chloride
  参考文献：
  名称：

  新型异双位卡宾-吡啶钯（II）氯乙烯基配合物的合成。不同钯乙烯基衍生物对炔基锡烷金属转移反应的比较

  摘要：

  摘要 DeC 活化的炔烃如二叔丁基乙炔二羧酸酯 (DTA) 或反应性更强的二甲基乙炔二羧酸酯 (DMA) 不与带有异双位碳烯-吡啶 (C- N) 作为旁观配体得到相应的乙烯基衍生物。为了制备这种类型的衍生物，我们采用了一种专门的合成方案，该方案基于用卡宾 - 吡啶氯化银配合物的卡宾 - 吡啶配体置换乙烯基钯吡啶 - 硫醚物种的不稳定吡啶 - 硫醚配体。然而，通过这种合成方案获得的新型卡宾 - 吡啶乙烯基配合物，如果与具有类似空间要求的其他钯乙烯基物种相比，显示出与乙炔基 - 锡烷的金属转移反应显着降低的反应性。

  DOI：

  10.1016/j.inoche.2013.03.026
• 作为产物：
  描述：

  2-(溴甲基)吡啶氢溴酸盐 、 1-(2,6-二异丙基苯基)-1H-咪唑 在 碳酸氢钠 作用下， 反应 1.75h， 以91%的产率得到1-(2,6-diisopropylphenyl)-3-(pyridin-2-ylmethyl)-1H-imidazol-3-ium bromide
  参考文献：
  名称：

  Noels型NHC-钌配合物的机械合成及其在开环易位聚合中的应用

  摘要：

  球磨机的使用使各种N-芳基，N-烷基咪唑鎓盐和相应的NHC银（I）络合物的有效机械合成成为可能。钌通过机械化学进行重金属化可以快速进入（从1.5分钟到1小时）到与Noels型预催化剂具有相似结构的络合物。评估降冰片烯在不同溶剂（包括无毒溶剂）中的开环易位聚合反应中的配合物，发现其中一种与Noels催化剂相比具有很高的催化活性。

  DOI：

  10.1021/acs.organomet.0c00013

文献信息

• Bulky Picolyl Substituted NHC Ligands and Their Pd ⁰ Complexes
  作者：Stefan Warsink、Carien M. S. van Aubel、Jan J. Weigand、Shiuh‐Tzung Liu、Cornelis J. Elsevier

  DOI：10.1002/ejic.201000768

  日期：2010.12

  Heterobidentate N-heterocyclic carbene-picolyl ligands with various substitution patterns and their palladium(0) complexes have been synthesized in excellent yields via their corresponding silver(I) complexes. These complexes are among the first examples where substitution next to the coordinating nitrogen is evaluated systematically. The complexes have been studied by NMR and X-ray diffraction, confirming

  具有各种取代模式的杂双齿 N-杂环卡宾-甲基吡啶配体及其钯 (0) 配合物已通过其相应的银 (I) 配合物以优异的产率合成。这些复合物是系统评估配位氮旁边取代的第一个例子。已通过 NMR 和 X 射线衍射研究了配合物，证实了它们的双齿性质。该配合物是炔烃向Z-烯烃转移半氢化的活性预催化剂，其活性和选择性在很大程度上取决于吡啶甲基取代基。观察到高达 92% 的选择性。
• N-Functionalised heterocyclic carbene complexes of silver
  作者：Arran A. D. Tulloch、Andreas A. Danopoulos、Scott Winston、Sven Kleinhenz、Graham Eastham

  DOI：10.1039/b007504n

  日期：——

  N-Functionalised imidazol-2-ylidene carbene complexes of AgI have been prepared by interaction of the corresponding imidazolium salt with Ag2O in dichloromethane or 1,2-dichloroethane in the presence of molecular sieves or with Ag2CO3 in 1,2-dichloroethane. In an analogous way disilver(I) complexes of o-phenylenedimethylenebis(imidazol-2-ylidene) have been obtained. Their structures, as determined

  N功能化的咪唑-2-亚烷基卡宾通过将相应的咪唑盐与Ag 2 O相互作用制得Ag I的配合物。二氯甲烷 或者 1,2-二氯乙烷在分子筛或有Ag存在2 CO 3中1,2-二氯乙烷。以类似的方式，获得了邻苯二亚甲基双（咪唑-2-亚甲基）的disilver（I）络合物。它们的结构，由X射线晶体学，表明 卡宾 配体 充当 卡宾末端或作为两个不同金属原子之间的桥梁。在一种情况下，白银由两个卡宾 配体。在大多数具有结构特征的络合物中，金属中心采用线性几何结构，其中M–C（卡宾）键的长度为单键特征值的207–210 pm。
• Solving the challenging synthesis of highly cytotoxic silver complexes bearing sterically hindered NHC ligands with mechanochemistry
  作者：Audrey Beillard、François Quintin、Jérémie Gatignol、Pascal Retailleau、Jean-Luc Renaud、Sylvain Gaillard、Thomas-Xavier Métro、Frédéric Lamaty、Xavier Bantreil

  DOI：10.1039/d0dt00410c

  日期：——

  straightforward synthesis of a variety of silver(I) complexes featuring challenging NHC ligands. Sterically hindered including electron-poor or with very low solubility imidazolium salts were ground with silver(I) oxide to furnish heteroleptic or homoleptic complexes in high yields and short reaction times. The synthesis of heteroleptic bis-NHC silver(I) complexes was also performed for the first time in a

  使用球磨机可以直接合成具有挑战性NHC配体的各种银（I）配合物。包括电子贫乏或溶解度非常低的受阻位咪唑鎓盐与氧化银（I）一起研磨，以高收率和较短的反应时间提供杂配或均配的配合物。杂合双-NHC银的合成（I）复合物也是第一次在球磨机中进行。机械化学方法的效率和快速性使得能够生成空前的NHC银复合物文库，评估了其对HCT116结肠直肠癌细胞系的细胞毒性，为药物机械化学提供了一个罕见的例子。发现阳离子银配合物比中性类似物更有效，IC 50值低至21 nM，且比顺铂强256倍。
• Functionalised and chelate heterocyclic carbene complexes of palladium; synthesis and structural studiesElectronic supplementary information (ESI) available: crystallographic data and ORTEP plots for complexes 4, 7, 8 and 13. See http://www.rsc.org/suppdata/dt/b2/b209231j/
  作者：Arran A. D. Tulloch、Scott Winston、Andreas A. Danopoulos、Graham Eastham、Michael B. Hursthouse

  DOI：10.1039/b209231j

  日期：2003.2.11

  A series of picolyl-functionalised, [(C^N)PdXY], 1a, 2a, 3a and 4, pyridyl-functionalised, [(C–N)PdXY], 5a, 6, 7 and 8, methoxymethyl-functionalised, [(C^O)Pd(μ-X)X]2, 10, and trans-[(C^O)2PdX2], 11, and diethylcarbamoylmethyl-functionalised, trans-[(C^amide)2PdX2], 12, N-heterocyclic carbene (NHC) complexes of palladium(II), (C^N) = (3-R1)[1-(α-picolyl)imidazol-2-ylidene, (C–N) = (3-R1)[1-(2-pyridyl)imidazol-2-ylidene, R1 = But, mesityl, 2,6-Pri2C6H3, (C^O) = (3-R1)(1-methoxymethyl)imidazol-2-ylidene, R1 = 2,6-Pri2C6H3, (C^amide) = (3-R1)(1-diethylcarbamoylmethyl)imidazol-2-ylidene, R1 = 2,6-Pri2C6H3, Y = Me, X = Br or Cl, have been synthesised by interaction of (1,5-cod)PdXY or (1,5-cod)PdX2 with the corresponding silver NHC complexes, or (in certain cases) with the free functionalised NHC ligands. Derivatives of 1a, 2a, 3a and 5a were prepared by substitution of the halide X by weakly coordinating anions. The majority of the complexes described here were characterised by spectroscopic and diffraction methods and show that the (C–N) and (C^N) ligands act as chelates, while the methoxymethyl- and diethylcarbamoylmethyl-functions in 10, 11 and 12, respectively, are dangling. Derivatives of 5a in which the pyridine ring is substituted with electron withdrawing or bulky substituents show only minor variation of the pyridine–palladium distances.

  一系列吡啶基官能化，[(C^N)PdXY]、1a、2a、3a 和 4，吡啶基官能化，[(C–N)PdXY]、5a、6、7 和 8，甲氧基甲基官能化，[ (C^O)Pd(μ-X)X]2、10 和反式-[(C^O)2PdX2]、11 和二乙基氨基甲酰甲基官能化、反式-[(C^酰胺)2PdX2]、12、N -钯(II)的杂环卡宾(NHC)络合物，(C^N) = (3-R1)[1-(α-吡啶甲基)咪唑-2-亚基，(C–N) = (3-R1)[1-(2-吡啶基)咪唑-2-亚基，R1 = 但是，异丙叉，2,6-Pri2C6H3，(C^O) = (3-R1)(1-甲氧基甲基)咪唑-2-亚基，R1 = 2,6-Pri2C6H3, (C^酰胺) = (3-R1)(1-二乙基氨基甲酰基甲基)咪唑-2-亚基，R1 = 2,6-Pri2C6H3，Y = Me，X = Br 或 Cl，通过 (1,5-cod)PdXY 或 (1,5-cod)PdX2 与相应的银 NHC 配合物相互作用合成，或（在某些情况下）与游离功能化 NHC 配体。通过用弱配位阴离子取代卤化物X来制备1a、2a、3a和5a的衍生物。本文描述的大多数配合物均通过光谱和衍射方法进行了表征，并表明 (C–N) 和 (C^N) 配体充当螯合物，而甲氧基甲基和二乙基氨基甲酰甲基功能分别在 10、11 和 12 中，悬空。 5a 的衍生物，其中吡啶环被吸电子或大体积取代基取代，仅显示吡啶-钯距离的微小变化。
• The interaction between heteroditopic pyridine–nitrogen NHC with novel sulfur NHC ligands in palladium(0) derivatives: Synthesis and structural characterization of a bis-carbene palladium(0) olefin complex and formation in solution of an alkene–alkyne mixed intermediate as a consequence of the ligands hemilability
  作者：Luciano Canovese、Fabiano Visentin、Carlo Levi、Claudio Santo、Valerio Bertolasi

  DOI：10.1016/j.ica.2012.04.018

  日期：2012.7

  We have synthesized a new class of heteroditopic chelating ligands bearing the phenylthiomethyl group and variously substituted imidazole derivatives and the corresponding complexes [Pd(eta(2)-ma)(R-NHC-CH2-SPh) (ma = maleic anhydride; R = methyl, mesityl, di-i-propylphenyl). We have compared their chemical characteristics and reactivity with those of similar palladium(0) complexes bearing the R-NHC-CH2-Py ligands.The hemilability of the above-mentioned moieties is apparent when their palladium derivatives react with an excess of the same or different heteroditopic ligands. In these cases, we obtained complexes bearing maleic anhydride and two mono-coordinated heteroditopic ligands bound to the same metal center. However, at variance with the generally accepted opinion, precipitation of AgBr does not warrant the quantitative formation of the bis-heteroditopic Pd(0) derivative and in some cases, a reaction involving a heterogeneous equilibrium is observed.The reaction of the palladium(0) carbene-sulfur or carbene-nitrogen complexes with the alkyne dimethyl-2-butynedioate (dmbd) to give palladacyclometallate derivatives is not always warranted and formation of the intermediate [Pd(eta(2)-ma)(eta(2)-dmdb)(kappa(1)-Mes-NHC-CH2-SPh)] is detected only in one case.Finally, we have carried out a diffractometric study on the solid-state structures of two derivatives and in particular we describe the configurations of the complex [Pd(eta(2)-ma)(kappa(1)-Me-NHC-CH2-SPh)(2)] and of [Pd(eta(2)-ma)(Me-NHC-CH2-SPh)]. (C) 2012 Elsevier B.V. All rights reserved.