2,3-bis(diphenylphosphino)quinoxaline | 1203710-23-9

• 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: 2,3-bis(diphenylphosphino)quinoxaline
• 英文别名: 2,3-bis(diphenylphosphanyl)quinoxaline；1,2-bis(diphenylphosphino)quinoxaline；dppq；dppQx；(3-Diphenylphosphanylquinoxalin-2-yl)-diphenylphosphane
• CAS: 1203710-23-9
• 化学式: C₃₂H₂₄N₂P₂
• 分子量: 498.503
• InChiKey: MZSWOLXBZKTHIO-UHFFFAOYSA-N

物化性质

• 沸点：
  620.5±55.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.2
• 重原子数：
  36
• 可旋转键数：
  6
• 环数：
  6.0
• 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

• 作为反应物：
  描述：

  bis(acetonitrile)decacarbonyltriosmium 、 2,3-bis(diphenylphosphino)quinoxaline 以 二氯甲烷 、 甲苯 为溶剂， 生成 1,1-Os3(CO)10(2,3-bis(diphenylphosphino)quinoxaline)
  参考文献：
  名称：

  包含杂环配体2,3-双-（二苯基膦基）喹喔啉（dppq）的新簇化合物：dppq的配体异构化和晶体结构，异构簇Os 3（CO）10（dppq）和HOs 3（CO）9 [μ-2,3-PHP（η 1 -C 6 ħ 4）（PH 2 P）喹喔啉]

  摘要：

  在室温下用二膦配体2,3-双（二苯基膦基）喹喔啉（dppq）处理不稳定簇1,2-Os 3（CO）10（MeCN）2（1）得到1,2-Os 3（CO ）10（dppq）（2b）作为配体取代的动力学产物，产率为84％。图2b异构化成热力学更稳定的dppq-螯合簇1,1 -锇3（CO）10（dppq）（图2c），其在温度低于358 K. CO下的唯一可观察到的产物为转化的动力学图2b  →  2C有无在CDCl中通过NMR光谱进行了研究3在323–353 K的温度范围内，发现该反应的速率定律在2b中是一阶的。计算的活化参数[ΔH ≠  = 25.4（4）kcal / mol；ΔS ≠  = -3（1）eu]支持分子内异构化方案，该方案涉及膦和CO基团围绕簇多面体的迁移。dppq配体在同构Os 3（CO）10（dppq）簇中的位置已通过X射线晶体学和31 P NMR光谱确定。2c在366 nm处发生光解会导致CO损失和Ph

  DOI：

  10.1016/j.jorganchem.2011.01.019
• 作为产物：
  描述：

  2,3-二氯喹喔啉 、 二苯基膦 在 正丁基锂 作用下， 以 正己烷 、 四氢呋喃 为溶剂， 反应 1.0h， 以85%的产率得到2,3-bis(diphenylphosphino)quinoxaline
  参考文献：
  名称：

  包含杂环配体2,3-双-（二苯基膦基）喹喔啉（dppq）的新簇化合物：dppq的配体异构化和晶体结构，异构簇Os 3（CO）10（dppq）和HOs 3（CO）9 [μ-2,3-PHP（η 1 -C 6 ħ 4）（PH 2 P）喹喔啉]

  摘要：

  在室温下用二膦配体2,3-双（二苯基膦基）喹喔啉（dppq）处理不稳定簇1,2-Os 3（CO）10（MeCN）2（1）得到1,2-Os 3（CO ）10（dppq）（2b）作为配体取代的动力学产物，产率为84％。图2b异构化成热力学更稳定的dppq-螯合簇1,1 -锇3（CO）10（dppq）（图2c），其在温度低于358 K. CO下的唯一可观察到的产物为转化的动力学图2b  →  2C有无在CDCl中通过NMR光谱进行了研究3在323–353 K的温度范围内，发现该反应的速率定律在2b中是一阶的。计算的活化参数[ΔH ≠  = 25.4（4）kcal / mol；ΔS ≠  = -3（1）eu]支持分子内异构化方案，该方案涉及膦和CO基团围绕簇多面体的迁移。dppq配体在同构Os 3（CO）10（dppq）簇中的位置已通过X射线晶体学和31 P NMR光谱确定。2c在366 nm处发生光解会导致CO损失和Ph

  DOI：

  10.1016/j.jorganchem.2011.01.019
• 作为试剂：
  描述：

  2-溴吡啶 、 2,4,6-三甲基苯胺 在 tris-(dibenzylideneacetone)dipalladium(0) 、 2,3-bis(diphenylphosphino)quinoxaline 、 potassium tert-butylate 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以64%的产率得到N-mesitylpyridin-2-amine
  参考文献：
  名称：

  Comparison of the reactivity of 2-amino-3-chloro- and 2,3-dichloroquinoxalines towards Ph2PH and Ph2PLi and of the properties of diphenylphosphanyl-quinoxaline P,N and P,P ligands

  摘要：

  The synthesis of quinoxaline P,N ligands by monoamination of 2,3-dichloroquinoxaline (1) to 2-amino-3-chloroquinoxalines 2a,b and the subsequent substitution of chlorine by a diphenylphosphanyl group was studied. Whereas the reaction of 2a,b with Ph2PH in the presence (or absence) of catalytic amounts of palladium acetate furnished only minor amounts of the expected ligands in favor of tetraphenyldiphosphane and dechlorinated quinoxalines, the coupling with Ph2PLi in ether provided the novel NH-functional P,N hybrid ligands 3a,b with a quinoxaline scaffold in moderate to good yields. 3a is slightly and 3b somewhat more sensitive to air oxidation, leading to the P-oxides 4a,b. The more reactive 1 forms with Ph2PH only a small amount of 2-chloro-3-diphenylphosphanylquinoxaline 5 and traces of the quinoxaline-bis(phosphane) 6. The main products are 2,2'-bis(quinoxaline) and Ph2PCl, which converts residual Ph2PH into tetraphenyldiphosphane. The coupling with Ph2PLi in diethyl ether, however, gave in a fast reaction high yields of 6, exceeding those of 3a,b, with interfering NH functions. Semi-empirical quantum chemical calculations (PM6) illuminate the background of the air sensitivity of 3a,b, whereas the recently reported 6 is air stable. Preliminary studies for use of the ligands in catalysis with the air-stable 6, showed moderate to good yields in the Pd-catalyzed C-N cross coupling of 2-bromopyridine with mesityl amine. Complex formation was confirmed by isolation of the Pd complex 7. The structure elucidation of the new compounds is based on conclusive NMR data and crystal structure analyses for 2b, 3a, 4a and 4b. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2012.08.089

文献信息

• Cytotoxic (<i>cis</i>,<i>cis</i>-1,3,5-triaminocyclohexane)ruthenium(<scp>ii</scp>)-diphosphine complexes; evidence for covalent binding <i>and</i> intercalation with DNA
  作者：Dan E. Wise、Aimee J. Gamble、Sham W. Arkawazi、Paul H. Walton、M. Carmen Galan、Michael P. O'Hagan、Karen G. Hogg、Joanne L. Marrison、Peter J. O'Toole、Hazel A. Sparkes、Jason M. Lynam、Paul G. Pringle

  DOI：10.1039/d0dt02612c

  日期：——

  with biologically relevant duplex and quadruplex DNA models correlate with the activity observed with A549, A2780 and 293T cell lines, and the degree of activity was found to be sensitive to the chelating diphosphine ligand. A label-free ptychographic cell imaging technique recorded cell death processes over 4 days. The Ru(II) cis-tach diphosphine complexes exhibit anti-proliferative effects, in some cases

  我们报告了具有通式 [RuCl( cis -tach)(diphosphine)] + ( cis -tach = cis – cis -1,3,5 - triaminocyclohexan) 的细胞毒性钌 ( II ) 配合物，其特征在于1 H, 13 C和31 P 1 H} NMR光谱、质谱、X射线晶体学和元素分析。研究了活性物质的水合动力学和稳定性，表明氯配体在 298 K 下被水取代，一级速率常数为 10 -2 –10 -3 s -1，非常适合作为抗肿瘤剂的潜在临床用途。与生物相关双链和四链 DNA 模型的强相互作用与在 A549、A2780 和 293T 细胞系中观察到的活性相关，并且发现活性程度对螯合二膦配体敏感。一种无标记的 ptychographic 细胞成像技术记录了超过 4 天的细胞死亡过程。Ru( II ) cis- tach 二膦配合物表现出抗增殖作用，在某些情况下优于顺铂和其他细胞毒性钌配合物。
• CATALYST FOR CROSS-COUPLING REACTION, AND PROCESS FOR PRODUCTION OF AROMATIC COMPOUND USING THE SAME
  申请人：Nakamura Masaharu

  公开号：US20110152523A1

  公开（公告）日：2011-06-23

  The present invention provides a process for efficiently producing an alkylated aromatic compound in good yield, by a cross-coupling reaction between an alkyl halide and an aromatic magnesium reagent. A process for producing an aromatic compound represented by Formula (1): R—Ar′  (1) wherein R is a hydrocarbon group, and Ar′ is an aryl group; the process comprising: reacting a compound represented by Formula (2): R—X  (2) wherein X is a halogen atom, and R is as defined above, with a magnesium reagent represented by Formula (3): Ar′—MgY  (3) wherein Y is a halogen atom, and Ar′ is as defined above, in the presence of a catalyst for cross-coupling reactions comprising an iron compound and a bisphosphine compound represented by Formula (4): wherein Q is a divalent group derived from an aromatic ring by removing two hydrogen (H) atoms on adjacent carbon atoms; and each Ar is independently an aryl group.

  本发明提供了一种高效产生烷基芳香化合物的方法，通过烷基卤化物和芳香镁试剂之间的交叉偶联反应，以良好的产率产生烷基芳香化合物的方法，所述方法包括：将由式（2）表示的化合物：R—X（2）其中X是卤素原子，R如上所定义，与由式（3）表示的镁试剂：Ar′—MgY（3）其中Y是卤素原子，Ar′如上所定义，在交叉偶联反应的催化剂存在下反应，所述催化剂包括一种铁化合物和一种由式（4）表示的双膦化合物：其中Q是通过去除相邻碳原子上的两个氢（H）原子从芳香环中衍生的二价基团；每个Ar都是独立的芳基团。
• Photoinduced Synthesis of Bisphosphinated Quinoxalines via Radical Cyclization of <i>o</i> ‐Diisocyanoarenes with Diphosphines
  作者：Yuki Yamamoto、Akiya Ogawa

  DOI：10.1002/asia.202201269

  日期：——

  A photoinduced synthesis of bisphosphinated quinoxalines was successfully achieved by using o-diisocyanoarenes with diphosphines. The novel reaction proceeds with good product selectivity, and can be conducted with easy operation, broad scope, and excellent atom-economy. Furthermore, this system can be applied to one-pot synthesis of PdII-quinoxaline complex.

  通过使用邻二异氰基芳烃和二膦成功地实现了双膦化喹喔啉的光诱导合成。该新反应产物选择性好，操作简单，适用范围广，原子经济性好。此外，该体系还可应用于一锅法合成Pd II-喹喔啉络合物。
• Serum-Stable Gold(III) Bisphosphine Complex Induces Mild Mitochondrial Uncoupling and In Vivo Antitumor Potency in Triple Negative Breast Cancer
  作者：Adedamola S. Arojojoye、Chibuzor Olelewe、Sailajah Gukathasan、Jong H. Kim、Hemendra Vekaria、Sean Parkin、Patrick G. Sullivan、Samuel G. Awuah

  DOI：10.1021/acs.jmedchem.3c00238

  日期：2023.6.22

  The preparation of cyclometalated complexes offers a path to stable materials, catalysts, and therapeutic agents. Here, we explore the anticancer potential of novel biphenyl organogold(III) cationic complexes supported by diverse bisphosphine ligands, Au-1–Au-5, toward aggressive glioblastoma and triple negative breast cancer cells (TNBCs). The [C^C] gold(III) complex, Au-3, exhibits significant tumor

  环金属化配合物的制备为稳定材料、催化剂和治疗剂提供了一条途径。在这里，我们探索了由不同双膦配体Au-1–Au-5支持的新型联苯有机金 (III) 阳离子复合物对侵袭性胶质母细胞瘤和三阴性乳腺癌细胞 (TNBC) 的抗癌潜力。 [C^C] 金 (III) 复合物Au-3在转移性 TNBC 小鼠模型中表现出显着的肿瘤生长抑制作用。值得注意的是， Au-3在 24 小时的相关治疗窗口内表现出良好的血清稳定性，并在过量L -GSH 存在的情况下发生变化。作用机制研究表明， Au-3可诱导线粒体解偶联、膜去极化和 G1 细胞周期停滞并促进细胞凋亡。据我们所知， Au-3是第一个在体内解偶联线粒体并抑制 TNBC 生长的联苯金-膦络合物。
• 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.