3-aminoquinoxalin-2-yldiphenylphosphine oxide | 1422179-79-0

• 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-aminoquinoxalin-2-yldiphenylphosphine oxide
• CAS: 1422179-79-0
• 化学式: C₂₀H₁₆N₃OP
• 分子量: 345.34
• InChiKey: SPCYCZMQDJUIRJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.85
• 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：
  68.87
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  2,3-二氯喹喔啉 在 氨 、 叔丁基锂 作用下， 以 N-甲基吡咯烷酮 、 乙醚 、 氘代氯仿 、 乙酸乙酯 、 正戊烷 为溶剂， 反应 3.08h， 生成 3-aminoquinoxalin-2-yldiphenylphosphine oxide
  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

• Aerobic oxidative C–H phosphorylation of quinoxalines under catalyst-free conditions
  作者：Qiaoyu Gan、Haibo Liu、Zeqi Jiang、Junmei Xia、Zhenhua Gao、Yongbiao Guo、Hongliang Wen

  DOI：10.1039/d3cc02848h

  日期：——

  We report an easily handled and environmentally friendly protocol for highly efficient phosphorylation of quinoxalines under mild and metal-free conditions employing air as the green oxidant via a dearomatization–rearomatization strategy.

  我们报告了一种在温和无金属条件下，通过脱芳烃-再芳烃化策略，采用空气作为绿色氧化剂，高效磷酸化喹喔啉类化合物的简便操作和环保方案。
• Inorganic ligand-supported Mo oxide as a hydrogen atom transfer photocatalyst for direct C(sp²)–H phosphorylation
  作者：Zeqi Jiang、Shuangfei Jiang、Jin Gao、Junmei Xia、Hongwei Yu、Lixin Ma、Xi Chen、Bo Chen、Xinghua Zhang、Wenchao Zhu

  DOI：10.1039/d4gc00589a

  日期：——

  temperature, without the addition of metals, bases, additives or external oxidants. A gram-scale reaction can occur in a low catalyst loading system. Moreover, the formulated photocatalyst showed excellent stability and reusability, and also exhibited satisfactory photo-reactivity under sunlight irradiation. The mechanistic investigations supported that the C(sp2)–P bond formation went through radical coupling

  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。