Synthesis of 2,3-bis(phenylphosphino)quinoxaline | 1304103-46-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: Synthesis of 2,3-bis(phenylphosphino)quinoxaline
• 英文别名: ppQx；Phenyl-(3-phenylphosphanylquinoxalin-2-yl)phosphane；phenyl-(3-phenylphosphanylquinoxalin-2-yl)phosphane
• CAS: 1304103-46-5
• 化学式: C₂₀H₁₆N₂P₂
• 分子量: 346.308
• InChiKey: UPNVVCIOQWMRQG-UHFFFAOYSA-N

物化性质

• 沸点：
  509.0±50.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2,3-二氯喹喔啉 、 phenylphosphine borane 在 正丁基锂 作用下， 以 四氢呋喃 、 环己烷 为溶剂， 反应 0.25h， 生成 Synthesis of 2,3-bis(phenylphosphino)quinoxaline 、 1,2-diphenyldiphosphane 、 苯基膦
  参考文献：
  名称：

  Synthesis, structure and spectroscopic properties of 2,3-bis(diphenylphosphino)quinoxaline (dppQx) and its copper(I) complexes

  摘要：

  Phosphinoquinoxalines were prepared by treatment of 2,3-dichloroquinoxaline (3) with phosphorus nucleophiles. The Arbuzov reaction of 3 with PPh(O-i-Pr)(2) gave a mixture of diastereomers of 2,3-(PPh(O) (O-i-Pr))(2)quinoxaline (6); the crystal structure of rac-6 was determined, but attempts at reduction to yield bis(phenylphosphino)quinoxaline 7 resulted in P-C cleavage and formation of phenylphosphine. The bis(secondary phosphine) 7 could be generated from 3 and LiPHPh(BH3), but was not isolated in pure form. Copper-catalyzed coupling of PHPh2 with 3 gave 2,3-bis(diphenylphosphino) quinoxaline (4, dppQx), whose coordination chemistry was investigated, with comparison to data for the analogous 1,2-bis(diphenylphosphino)benzene (dppBz) complexes. Reaction of dppQx with [Cu(NCMe)(4)][PF6] gave [Cu(dppQx)(2)][PF6] (8); CuCl yielded [Cu(dppQx)Cl](2) (9). Reaction of [Cu(NCMe)(4)][PF6] with one equiv of DPEphos, followed by one equiv of dppQx, gave [Cu(dppQx)(DPEphos)][PF6] (10). Ligand 4 and copper complexes 8 and 9 were crystallographically characterized. The UV-Vis spectra of dppQx and its copper complexes were red-shifted from those of the dppBz analogs; in contrast to results for the dppBz complexes, those of dppQx were not luminescent in solution. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2011.01.015

文献信息

• Synthesis, structure and spectroscopic properties of 2,3-bis(diphenylphosphino)quinoxaline (dppQx) and its copper(I) complexes
  作者：Matthew F. Cain、Samantha C. Reynolds、Brian J. Anderson、David S. Glueck、James A. Golen、Curtis E. Moore、Arnold L. Rheingold

  DOI：10.1016/j.ica.2011.01.015

  日期：2011.4

  Phosphinoquinoxalines were prepared by treatment of 2,3-dichloroquinoxaline (3) with phosphorus nucleophiles. The Arbuzov reaction of 3 with PPh(O-i-Pr)(2) gave a mixture of diastereomers of 2,3-(PPh(O) (O-i-Pr))(2)quinoxaline (6); the crystal structure of rac-6 was determined, but attempts at reduction to yield bis(phenylphosphino)quinoxaline 7 resulted in P-C cleavage and formation of phenylphosphine. The bis(secondary phosphine) 7 could be generated from 3 and LiPHPh(BH3), but was not isolated in pure form. Copper-catalyzed coupling of PHPh2 with 3 gave 2,3-bis(diphenylphosphino) quinoxaline (4, dppQx), whose coordination chemistry was investigated, with comparison to data for the analogous 1,2-bis(diphenylphosphino)benzene (dppBz) complexes. Reaction of dppQx with [Cu(NCMe)(4)][PF6] gave [Cu(dppQx)(2)][PF6] (8); CuCl yielded [Cu(dppQx)Cl](2) (9). Reaction of [Cu(NCMe)(4)][PF6] with one equiv of DPEphos, followed by one equiv of dppQx, gave [Cu(dppQx)(DPEphos)][PF6] (10). Ligand 4 and copper complexes 8 and 9 were crystallographically characterized. The UV-Vis spectra of dppQx and its copper complexes were red-shifted from those of the dppBz analogs; in contrast to results for the dppBz complexes, those of dppQx were not luminescent in solution. (C) 2011 Elsevier B.V. All rights reserved.