(3-chloroquinoxalin-2-yl)diphenylphosphine oxide | 1422179-84-7

• 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: (3-chloroquinoxalin-2-yl)diphenylphosphine oxide
• 英文别名: 2-chloro-3-diphenylphosphanylquinoxaline
• CAS: 1422179-84-7
• 化学式: C₂₀H₁₄ClN₂OP
• 分子量: 364.771
• InChiKey: GPVPHAXDBSYJEJ-UHFFFAOYSA-N

物化性质

• 沸点：
  567.7±50.0 °C(Predicted)
• 密度：
  1.37±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.92
• 重原子数：
  25.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  42.85
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  2-氯喹恶啉 、 Diphenylphosphine oxide 在 bis(tetrabutylammonium) hexamolybdate 作用下， 以 水 、 乙腈 为溶剂， 以77 %的产率得到(3-chloroquinoxalin-2-yl)diphenylphosphine oxide
  参考文献：
  名称：

  无机配体负载的 Mo 氧化物作为氢原子转移光催化剂用于直接 C(sp2)–H 磷酸化

  摘要：

  使用无机配体负载的 Mo 氧化物 ([N(C 4 H 9 ) 4 ] 2 [ Mo 6 O 19 ])作为氢原子转移（HAT）光催化剂。所开发的光驱动C(sp 2 )–P键形成方案可以在室温下的水基溶剂中提供多种具有优异官能团耐受性的产品，无需添加金属、碱、添加剂或外部氧化剂。克级反应可以在低催化剂负载量系统中发生。此外，配制的光催化剂表现出优异的稳定性和可重复使用性，并且在阳光照射下也表现出令人满意的光反应活性。机理研究表明C(sp 2 )-P键的形成是通过自由基偶联或自由基亲核加成途径进行的。

  DOI：

  10.1039/d4gc00589a

文献信息

• Metal-free direct C–H phosphonation of N-heterocycles with diphenylphosphine oxides under mild conditions
  作者：Zhao-Nan Cai、Ya-Ping Han、Yuecheng Zhang、Hong-Yu Zhang、Jiquan Zhao、Shang-Dong Yang

  DOI：10.1039/d3gc01251d

  日期：——

  Herein, metal-free phosphonation of N-heterocycles with diphenylphosphine oxides, promoted by easily available 1,5-diazabicyclo[5,4,0]undec-5-ene (DBU) in dimethyl carbonate (DMC) as a green solvent under an air atmosphere, is presented. This simple method can accommodate 1,2,4-triazine-3,5(2H,4H)-diones, quinoxalin-2(1H)-ones, quinoxalines and pyrazinones with diverse substituted diphenylphosphine oxides

  在此，在碳酸二甲酯（DMC）作为绿色溶剂中，通过容易获得的1,5-二氮杂双环[5,4,0]十一碳五烯（DBU）在有机溶剂中促进N-杂环与二苯基膦氧化物的无金属膦化。空气气氛，呈现。这种简单的方法可以容纳 1,2,4-三嗪-3,5(2 H ,4 H )-二酮、喹喔啉-2(1 H)-酮、喹喔啉和吡嗪酮与多种取代的二苯基膦氧化物，提供具有广泛官能团耐受性的独特单磷酸化 N-杂环，并且这些转化也可用于生物活性和药物分子的后修饰。除了不含金属和光催化剂以及利用环境空气作为氧化剂的可持续特征外，该方法有效地实现了克级转化，并且通过萃取和过滤而不是柱色谱分离产物。
• 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
  作者：Mohamed Shaker S. Adam、Ahmad Desoky Mohamad、Peter G. Jones、Markus K. Kindermann、Joachim W. Heinicke

  DOI：10.1016/j.poly.2012.08.089

  日期：2013.2

  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.
• Autoxidative C(<i>sp</i>²)–P Formation: Direct Phosphorylation of Heteroarenes under Oxygen, Metal-Free, and Solvent-Free Conditions
  作者：Kai Luo、Yao-Zhong Chen、Li-Xian Chen、Lei Wu

  DOI：10.1021/acs.joc.6b00592

  日期：2016.6.3

  We reveal here a direct autoxidative phosphorylation of heteroarenes induced by oxygen under metal-free and solvent-free conditions. This new methodology provides an economical, operationally simple, and environmentally friendly approach toward (Het)C(sp(2))-P formation with medium to excellent yields. Heteroarenes including thiazole and quinoxaline derivatives are applicable under standard conditions, which is testified via a radical mechanism.