5-(diphenylphosphino)-1-methyl-1H-imidazole | 1318212-69-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 5-(diphenylphosphino)-1-methyl-1H-imidazole
• 英文别名: 1-methylimidazol-5-yldiphenylphosphane；(1-methylimidazol-5-yl)diphenylphosphine；(3-Methylimidazol-4-yl)-diphenylphosphane；(3-methylimidazol-4-yl)-diphenylphosphane
• CAS: 1318212-69-9
• 化学式: C₁₆H₁₅N₂P
• 分子量: 266.282
• InChiKey: AKYZXQSQYHBFRE-UHFFFAOYSA-N

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：
  0.06
• 拓扑面积：
  17.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (tetrahydrothiophene)gold(I) chloride 、 氯仿 、 5-(diphenylphosphino)-1-methyl-1H-imidazole 、 水 以 二氯甲烷 为溶剂， 以58%的产率得到[((1-methylimidazol-5-yl)diphenylphosphane)AuCl]*1.5CHCl3*H2O
  参考文献：
  名称：

  Gold(I) Catalysts with Bifunctional P, N Ligands

  摘要：

  A series of phosphanes with imidazolyl substituents were prepared as hemilabile PN ligands. The corresponding gold(I) complexes were tested as bifunctional catalysts in the Markovnikov hydration of 1-octyne, as well as in the synthesis of propargylamines by the three component coupling reaction of piperidine, benzaldehyde, and phenylacetylene. While the activity in the hydration of 1-octyne was low, the complexes are potent catalysts for the three component coupling reaction. In homogeneous solution the conversions to the respective propargylamine were considerably higher than under aqueous biphasic conditions. The connectivity of the imidazolyl substituents to the phosphorus atom, their substitution pattern, as well as the number of heteroaromatic substituents have pronounced effects on the catalytic activity of the corresponding gold(I) complexes. Furthermore, formation of polymetallic species with Au-2, Au-3, and Au-4 units has been observed and the solid-state structures of the compounds [(5)(2)Au3Cl2]Cl and [(3c)(2)Au4Cl2]Cl-2 (3c = tris(2-isopropylimidazol-4(5)-yl phosphane, 5 = 2-tert-butylimidazol-4(5)-yldiphenyl phosphane) were determined. The gold(I) complexes of imidazol-2-yl phosphane ligands proved to be a novel source for bis(NHC)gold(I) complexes (NHC = N-heterocyclic carbene).

  DOI：

  10.1021/ic2011259
• 作为产物：
  描述：

  1-(di-tert-butylphosphino)-3-methyl-3H-imidazol-1-ium trifluoromethanesulfonate 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 5-(diphenylphosphino)-1-methyl-1H-imidazole
  参考文献：
  名称：

  N-磷酸化的咪唑鎓盐作为2和5磷酸化的咪唑和具有PNCN单元的新型咪唑-2-亚胺的前体

  摘要：

  实验已经证明1-或1，2-二取代的咪唑与二有机基磷（III）卤化物的反应是通过最初形成N-磷酸化的咪唑鎓盐而进行的。用强碱处理这些盐会相应地导致母体咪唑在2或5位发生磷酸化。在先前的情况下，形成咪唑-2-亚基作为中间体。在N1和N3原子上都带有空间要求或/和π供体基团的情况下，将1,3-二取代的咪唑鎓盐与NaN（SiMe 3）2进行去质子化反应可得到新的稳定的N-磷取代的Arduengo型卡宾。

  DOI：

  10.1021/jo101177h

文献信息

• Is the¹<i>J</i>_PSeCoupling Constant a Reliable Probe for the Basicity of Phosphines? A³¹P NMR Study
  作者：Udo Beckmann、Diyana Süslüyan、Peter C. Kunz

  DOI：10.1080/10426507.2010.547892

  日期：2011.10

  functionalized aryl substituents on the electron-donating ability and basicity of the phosphorus atoms in heteroaryl phosphines and diphosphines has been determined by the use of the direct 1JPSe coupling constants of the corresponding selenides. The generality of the use of 31P–77Se spin–spin coupling constants as probe for the basicity of phosphines is discussed as well as the scope and limits of this concept

  摘要 不同的杂芳基和官能化芳基取代基对杂芳基膦和二膦中磷原子的给电子能力和碱性的影响已通过使用相应硒化物的直接 1JPSe 偶联常数确定。讨论了使用 31P-77Se 自旋-自旋耦合常数作为膦碱度的探针的一般性以及该概念的范围和限制。图形概要
• N-Phosphorylated Imidazolium Salts as Precursors to 2- and 5-Phosphorylated Imidazoles and New Imidazol-2-ylidenes Featuring the PNCN Unit
  作者：Anatolii P. Marchenko、Heorgii N. Koidan、Anastasiya N. Huryeva、Evgeniy V. Zarudnitskii、Aleksandr A. Yurchenko、Aleksandr N. Kostyuk

  DOI：10.1021/jo101177h

  日期：2010.11.5

  It has been experimentally proven that the reaction of 1- or 1,2-disubstituted imidazoles with diorganylphosphorus(III) halides proceeds via initial formation of N-phosporylated imidazolium salts. Treatment of these salts with strong bases results in phosphorylation of the parent imidazoles at the 2- or 5-positions, correspondingly. In a previous case, imidazol-2-ylidenes are formed as intermediates

  实验已经证明1-或1，2-二取代的咪唑与二有机基磷（III）卤化物的反应是通过最初形成N-磷酸化的咪唑鎓盐而进行的。用强碱处理这些盐会相应地导致母体咪唑在2或5位发生磷酸化。在先前的情况下，形成咪唑-2-亚基作为中间体。在N1和N3原子上都带有空间要求或/和π供体基团的情况下，将1,3-二取代的咪唑鎓盐与NaN（SiMe 3）2进行去质子化反应可得到新的稳定的N-磷取代的Arduengo型卡宾。
• Gold(I) Catalysts with Bifunctional P, N Ligands
  作者：Corinna Wetzel、Peter C. Kunz、Indre Thiel、Bernhard Spingler

  DOI：10.1021/ic2011259

  日期：2011.8.15

  A series of phosphanes with imidazolyl substituents were prepared as hemilabile PN ligands. The corresponding gold(I) complexes were tested as bifunctional catalysts in the Markovnikov hydration of 1-octyne, as well as in the synthesis of propargylamines by the three component coupling reaction of piperidine, benzaldehyde, and phenylacetylene. While the activity in the hydration of 1-octyne was low, the complexes are potent catalysts for the three component coupling reaction. In homogeneous solution the conversions to the respective propargylamine were considerably higher than under aqueous biphasic conditions. The connectivity of the imidazolyl substituents to the phosphorus atom, their substitution pattern, as well as the number of heteroaromatic substituents have pronounced effects on the catalytic activity of the corresponding gold(I) complexes. Furthermore, formation of polymetallic species with Au-2, Au-3, and Au-4 units has been observed and the solid-state structures of the compounds [(5)(2)Au3Cl2]Cl and [(3c)(2)Au4Cl2]Cl-2 (3c = tris(2-isopropylimidazol-4(5)-yl phosphane, 5 = 2-tert-butylimidazol-4(5)-yldiphenyl phosphane) were determined. The gold(I) complexes of imidazol-2-yl phosphane ligands proved to be a novel source for bis(NHC)gold(I) complexes (NHC = N-heterocyclic carbene).