2-(二苯基膦基)-1-甲基-1H-咪唑 | 150404-18-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 中文名称: 2-(二苯基膦基)-1-甲基-1H-咪唑
• 英文名称: (1-methylimidazol-2-yl)diphenylphosphine
• 英文别名: 2-(diphenylphosphino)-1-methylimidazole；1-methyl-2-diphenylphosphinoimidazole；2-(diphenylphosphino)-1-methyl-1H-imidazole；(1-methylimidazol-2-yl)-diphenylphosphane
• CAS: 150404-18-5
• 化学式: C₁₆H₁₅N₂P
• mdl: MFCD00194806
• 分子量: 266.282
• InChiKey: XETUDUREHZVDEM-UHFFFAOYSA-N

物化性质

• 熔点：
  73 °C
• 沸点：
  428.7±28.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.062
• 拓扑面积：
  17.8
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 储存条件：
  | 室温 |

反应信息

• 作为反应物：
  描述：

  2-(二苯基膦基)-1-甲基-1H-咪唑 以 二氯甲烷 、 丙酮 为溶剂， 反应 73.0h， 生成 [Au^I(1-methyl-2-diphenylphosphino-3-methylimidazolium)Cl-AuCl₂-Au(1-methyl-2-diphenylphosphino-3-methylimidazolium)Cl]AuCl₄
  参考文献：
  名称：

  The ionic mononuclear and trinuclear Au(I)-complexes ligated by phosphine-functionalized ionic liquids: Synthesis, characterization, and catalysis to hydration of phenylacetylene

  摘要：

  A series of ionic Au(I)-complexes ligated by the phosphine-functionalized ionic liquids were synthesized and characterized, which are composed of the Au(I)-complex cation and the counteranion of OTf , AuCl4, or PF6-, respectively. The single crystal X-ray diffraction analyses show that the Au(I)-centered vector in 1A, 1B, 2A, 3A, and 4A all possess the slightly twisted linear geometry, and in each individual the Au(I)-center is coordinated by one chlorine and one imidazolium-based phosphine. The aggregation of 1B in acetone can lead to the formation of the trinuclear Au(I)-complex of 1C due to the aurophilic Au(I)-Au(I) interaction, the electrostatic attraction, and the steric preference. When these ionic Au-complexes were employed as precatalysts for hydration of phenylacetylene in aqueous-methanol media, the reaction proceeded selectively according to Markovnikov's rule with moderate to high yields of acetophenone. The highest activities were achieved over 2A with hydrophobic PF6- as the counteranion and the trinuclear 1C under mild conditions (75 degrees C, 2 h), in conjunction with the additive of proton acid H2SO4. The ion-pair effect on the catalytic performance of the corresponding Au(I)-complexes, coming from the phosphine-ligated cations and the counteranions, were investigated. (C) 2014 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2014.04.005
• 作为产物：
  描述：

  二苯基溴膦 在 吡啶 、 三乙胺 作用下， 生成 2-(二苯基膦基)-1-甲基-1H-咪唑
  参考文献：
  名称：

  三价磷卤化物对唑类的 C-磷酸化

  摘要：

  摘要 开发了三价卤化磷在吡啶溶液中C-磷酸化唑类的简单方法。Hetaryldihalogen、dihetarylhalogen-、trihetarylphosphines 已被合成，它们被转化为新型的 P(III) 和 P(IV) 衍生物。发现了由杂芳基残基的影响规定的它们的反应能力的特征。

  DOI：

  10.1080/10426509608545194
• 作为试剂：
  描述：

  1-(4-溴苯基)辛烷 、 苯硼酸 在 potassium phosphite 、 2-(二苯基膦基)-1-甲基-1H-咪唑 、 palladium dichloride 作用下， 以 乙醇 、 水 为溶剂， 反应 3.0h， 以94%的产率得到4-正辛基联苯
  参考文献：
  名称：

  1-甲基咪唑基膦配体在钯催化的Suzuki偶联反应中的催化活性

  摘要：

  使用PdCl 2作为催化剂测试了三个基于N-甲基咪唑的膦配体在Suzuki偶联反应中的催化活性。结果表明，所有三种膦配体均对铃木反应表现出优异的活性，并且随着咪唑基团数量的增加，催化活性降低。版权所有©2014 John Wiley＆Sons，Ltd.

  DOI：

  10.1002/aoc.3249

文献信息

• A 4,5-Diphosphino-Substituted Imidazolium Salt: A Building Block for the Modular Synthesis of Mixed Diphosphine-NHC Heterometallic Complexes
  作者：Javier Ruiz、Alejandro F. Mesa

  DOI：10.1002/chem.201200031

  日期：2012.4.10

  Fused in the same molecule! An N‐heterocyclic carbene and a diphosphine are generated and used in the modular synthesis of a variety of target heterometallic complexes. The experimental approach involves formation of a unique 4,5‐bis(diphenylphosphino)‐1,3‐dimethyl‐imidazolium salt, simply by starting from 1‐methylimidazole (see scheme; M1=Cr, Mn; M2=Au, Rh, Pd; LiHMDS=LiN(SiMe3)2).

  融合在同一分子中！N-杂环卡宾和二膦生成并用于各种目标杂金属配合物的模块合成。实验方法涉及简单地从1-甲基咪唑开始形成独特的4,5-双（二苯基膦基）-1,3-二甲基咪唑鎓盐（参见方案; M 1 = Cr，Mn; M 2 = Au，Rh ，Pd； LiHMDS ＝ LiN（SiMe 3）2）。
• Nickel-catalyzed electrocarboxylation of allylic halides with CO₂
  作者：La-Xia Wu、Fang-Jie Deng、Lin Wu、Huan Wang、Tai-jie Chen、Ye-Bin Guan、Jia-Xing Lu

  DOI：10.1039/d1nj02006d

  日期：——

  Nickel-catalyzed regioselective electrocarboxylation of allylic halides with CO2 at atmospheric pressure has been developed by adjusting reaction parameters, including catalyst, solvent, temperature and additive. β,γ-Unsaturated carboxylic acids were obtained in moderate to good yields and with high chain selectivity. This reaction shows tolerance to functional groups. In addition, cyclic voltammetry

  通过调整包括催化剂、溶剂、温度和添加剂在内的反应参数，已开发出镍催化的烯丙基卤化物与 CO 2在大气压下的区域选择性电羧化反应。以中等至良好的产率和高链选择性获得了 β,γ-不饱和羧酸。该反应显示出对官能团的耐受性。此外，还进行了循环伏安法以提供镍催化的 CO 2烯丙基化的可能机制。
• Preparation of new half sandwich ruthenium arene complexes with aminophosphines as potential chemotherapeutics
  作者：Cristina Aliende、Mercedes Pérez-Manrique、Félix A. Jalón、Blanca R. Manzano、Ana M. Rodríguez、José Vicente Cuevas、Gustavo Espino、Mª Ángeles Martínez、Anna Massaguer、Marta González-Bártulos、Rafael de Llorens、Virtudes Moreno

  DOI：10.1016/j.jinorgbio.2012.07.022

  日期：2012.12

  Aminophosphines 2-(diphenylphosphino)-1-methylimidazole (dpim) and diphenyl-2-pyridylphosphine (PPh2py) have been used to prepare two series of Ru(II) arene complexes of formulae [(η6-p-cymene)Ru(κ2-O,O′-X)(κ1-P-dpim)]Y (series a: 1a·Y–3a·Y) and [(η6-p-cymene)Ru(κ2-O,O′-X)(κ1-P-PPh2py)]Y (series b: 1b·Y–3b·Y) (where X = acac, acetylacetonate; bzac, benzoyl acetonate; dbzm, dibenzoyl methanoate; Y = BF4

  氨基膦-2-（二苯基膦基）-1-甲基咪唑（DPIM）和二苯基-2-吡啶基膦（PPH 2 PY）已被用来制备两个系列的Ru（II）芳烃式配合物[（η 6 - p -cymene）茹（κ 2 - O，O' -X）（κ 1 - p -dpim）] Y（系列：1A·Y -图3a·Y）和[（η 6 - p -cymene）的Ru（κ 2 - O， O' -X）（κ 1 - P -PPh 2 PY）] Y（系列b：1B·Y -图3b·Y）（其中X = acac，乙酰丙酮酸酯; bzac，苯甲酰基丙酮酸酯; dbzm，二苯甲酰甲烷酸酯; Y = BF 4，BPh 4）。的结构1A·BF 4，1A·BPH 4，图3a·BF 4，图1b·BPH 4和图3b·BPH 4通过X射线衍射确定。四氟硼酸盐衍生物比四苯基硼酸盐对应物更易溶于有机溶剂。五BF 4 -衍生物（除了不稳定1B·BF 4）被选择，以评估细胞毒
• Monosubstituted, Anionic Imidazolyl Ligands from N−H NHC Precursors and Their Activity in Pd‐Catalyzed Cross‐Coupling Reactions
  作者：Erin E. Martinez、Christopher A. Jensen、Alexandra J. S. Larson、Karissa C. Kenney、Kyle J. Clark、S. Hadi Nazari、Gabriel A. Valdivia‐Berroeta、Stacey J. Smith、Daniel H. Ess、David J. Michaelis

  DOI：10.1002/adsc.202000483

  日期：2020.7.29

  We report that treatment of several 2‐diphenylphosphinoimidazoles with Pd(II) salts generates monosubstituted N−H NHC−Pd complexes via insertion into the C−P bond. Removal of the N−H proton in situ leads to anionic (X‐type) or imidazolyl‐Pd complexes that are highly stable and catalytically active, achieving up to 340,000 turnovers at 1 ppm catalyst loading in Suzuki‐Miyaura reactions. DFT‐calculated

  我们报告说，用Pd（II）盐处理几种2-diphenylphosphinoimidazoles会通过插入CP键生成单取代的NH NHC-Pd复合物。原位除去NH质子会生成高度稳定且具有催化活性的阴离子（X型）或咪唑基-Pd络合物，在Suzuki-Miyaura反应中，当催化剂负载1 ppm时，可实现高达340,000的周转率。DFT计算的空间小的配体的Tolman电子参数表明，这些配体比传统的NHC显着增加了供体，这为快速交叉偶联催化提供了理论依据。Sonogashira反应中也显示出优异的反应性。
• Intramolecularly Stabilised Group 10 Metal Stannyl and Stannylene Complexes: Multi-pathway Synthesis and Observation of Platinum-to-Tin Alkyl Transfer
  作者：Stefan Warsink、Eric J. Derrah、Cornelis A. Boon、Yves Cabon、Jeroen J. M. de Pater、Martin Lutz、Robertus J. M. Klein Gebbink、Berth-Jan Deelman

  DOI：10.1002/chem.201404071

  日期：2015.1.19

  indicating that both kinetic and thermodynamic products can be isolated for Pt, whereas for Pd only methylstannylene complexes are isolated. Oxidative addition of RSnCl3 (R=Me, Bu, Ph) to M0 precursors (M=Pd or Pt) in the presence of P^N ligands results in diphosphinostannylene pincer complexes trans‐[MCl(P^N)2SnCl(R)}][SnCl4R], which are structurally similar to the products from SnCl2 insertion. This showed

  [PdClMe（P ^ N）2 ]与SnCl 2反应，然后进行Cl吸附导致明显的PdC键活化，从而导致甲基亚锡基物种反式-[PdCl （P ^ N）2 SnClMe}] [BF 4 ] （P ^ N =二芳基膦基-N-杂环）。与此相反，铂类似物与的SnCl的反应2根引线与Pt  Cl键的激活，从而导致methylplatinum物种反式- [PTME（P ^ N）2的SnCl 2 }] [BF 4]。随着时间的流逝，它们异构化为甲基亚锡基物质，表明可以分离出Pt的动力学和热力学产物，而对于Pd，则只能分离出甲基亚锡的配合物。在存在P ^ N配体的情况下，将RSnCl 3（R = Me，Bu，Ph）氧化添加到M 0前体（M = Pd或Pt）会导致二膦锡锡夹钳配合物反式-[MCl （P ^ N）2 SnCl （R）}] [SnCl 4 R]，其结构与插入SnCl 2的产物相似。这表明，除了RSnCl的3到M