o-dimethylaminophenyl(8-quinolynyl)amine | 369364-26-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: o-dimethylaminophenyl(8-quinolynyl)amine
• 英文别名: 2-N,2-N-dimethyl-1-N-quinolin-8-ylbenzene-1,2-diamine
• CAS: 369364-26-1
• 化学式: C₁₇H₁₇N₃
• 分子量: 263.342
• InChiKey: DIUYXCZMZQIZPP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  28.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  o-dimethylaminophenyl(8-quinolynyl)amine 、 nickel diacetate 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以68%的产率得到
  参考文献：
  名称：

  喹啉基NNN-镍镍（II）配合物的合成：鲁棒和改进的催化剂体系，用于卤代烷与卤代烷的C–H键烷基化

  摘要：

  The quinoline-based pincer nickel(II) complexes kappa(N),kappa(N),kappa(N) -{R2N-C6H4-(mu-N)-C9H6N}NiX (((NNNQ)-N-R2)NiCl: R = Me) 2a; R = Et, 2b) were synthesized by the reaction of the ligand precursors ((NNNQ)-N-R2)H (R = Me, 1a; R = Et, 1b) with (DME)NiCl2 in the presence of Et3N. Similarly, the pincer mickel(II) derivatives ((NNNQ)-N-R2)NiX (R = Me, X = Br, 3a; R = Et, X = Br, 3b; R = Me, X = OAc, 4a) were obtained by treatment of the ligands ((NNNQ)-N-R2)H with the nickel precursor (THF)(2)NiBr2 or Ni(QAc)(2). All of these complexes were characterized by H-1 and C-13 NMR spectroscopy as well as by elemental analysis. Further, the molecular structures of 2a and 3a,b were elucidated by X-ray crystallography. Complex 2a is found to be an efficient catalyst for the direct C-H bond alkylation of substituted benzothiazoles and oxazoles with various unactivated alkyl halides containing beta-hydrogens under mild reaction conditions. The catalyst 2a is very robust and was recycled and reused five times for the alkylation reaction without a decrease in its catalytic activity. Preliminary studies reveal that the catalyst 2a acts as an active catalyst and the alkylation reaction appears to operate via a radical pathway.

  DOI：

  10.1021/acs.organomet.6b00201
• 作为产物：
  描述：

  8-氨基喹啉 、 2-溴-N,N-二甲基苯胺 在 tris-(dibenzylideneacetone)dipalladium(0) 、 sodium t-butanolate 作用下， 生成 o-dimethylaminophenyl(8-quinolynyl)amine
  参考文献：
  名称：

  配体调查结果鉴定了铱的 PNP 钳形配合物作为末端炔烃脱氢硼化的长寿命和化学选择性催化剂†

  摘要：

  继关于成功使用铱的 SiNN 钳形配合物作为末端炔烃 (DHBTA) 脱氢硼化为炔基硼酸盐的催化剂的报告之后，这项工作研究了各种相关钳形配体在 DHBTA 中的支持作用。配体选择包括新的和以前报道的配体，旨在探索 SiNN 框架（8-（2-二异丙基甲硅烷基苯基）氨基喹啉）的系统变化。令人惊讶的是，只有二芳基氨基/双（膦） PNP 系统显示出任何 DHBTA 反应性。筛选中使用的特定 PNP 配体（带有两个二异丙基膦基侧供体）显示 DHBTA 活性低于 SiNN。然而，利用 PNP 系统提供的配体优化机会，通过磷取代的变化导致发现了一种催化剂，其活性、寿命和范围远远超过了原始 SiNN 原型。在模型 PNP 系统中制备了几种 Ir 配合物，并作为催化循环中的潜在中间体进行了评估。其中，(PNP)Ir 二硼基络合物和硼基亚乙烯基络合物显示出催化能力较差，因此可能不是催化循环的一部分。

  DOI：

  10.1039/c5sc02161h

文献信息

• Synthesis of Aliphatic Carboxamides Mediated by Nickel NN₂ -Pincer Complexes and Adaptation to Carbon-Isotope Labeling
  作者：Karoline T. Neumann、Aske S. Donslund、Thomas L. Andersen、Dennis U. Nielsen、Troels Skrydstrup

  DOI：10.1002/chem.201804077

  日期：2018.10.9

  reagents, stoichiometric carbon monoxide and amines is described for the first time, which can be adapted to late‐stage carbon‐isotope labeling. This work expands the scope of the highly established palladium‐promoted version of the reaction, by allowing carbon‐sp3 fragments to take part in the three‐component reaction. Finally, the results obtained show a remarkable effect of the pincer ligand for

  首次介绍了使用NN 2钳形镍配合物，烷基锌试剂，化学计量一氧化碳和胺开发镍介导的氨基羰基化反应的方法，该方法可用于后期碳同位素标记。通过允许碳sp 3片段参与三组分反应，这项工作扩展了高度确立的钯促进反应的范围。最后，获得的结果显示了钳型配体在用胺进行的还原消除步骤中的显着效果，随后进行了13 C NMR光谱研究。
• Pincer-like Amido Complexes of Platinum, Palladium, and Nickel
  作者：Jonas C. Peters、Seth B. Harkins、Steven D. Brown、Michael W. Day

  DOI：10.1021/ic010336p

  日期：2001.9.1

  presented. Lithium amide 5 was transmetalated by TlOTf to afford the thallium(I) amido complex [Tl][BQA] (6). An X-ray structural study of 6 shows it to be a 1:1 complex of the BQA ligand and Tl. Entry into the group 10 chemistry of the parent ligand 1 was effected by both protolytic and metathetical strategies. Thus, the divalent chloride complexes (BQA)PtCl (7), (BQA)PdCl (8), and (BQA)NiCl (9) were prepared

  配体双（8-喹啉基）胺（BQAH，1），（2-吡啶-2-基-乙基）-（8-喹啉基）胺（2-吡啶-2-基-乙基-QAH，2），o高产率地制备了-二甲基氨基苯基（8-喹啉基）胺（o-（NMe2）Ph-QAH，3）和3,5-二甲基苯基（8-喹啉基）胺（3,5-Me2Ph-QAH，4）钯催化的偶联反应合成芳基卤化物和胺前体。在甲苯中用nBuLi对1进行去质子化反应得到氨基酰胺锂复合物[Li] [BQA]（5），其二聚体固态晶体结构呈现出来。通过TlOTf对酰胺化锂5进行金属化处理，得到the（I）酰胺基络合物[Tl] [BQA]（6）。对6的X射线结构研究表明，它是BQA配体和T1的1：1配合物。母体配体1进入第10组化学反应是通过蛋白水解和复分解策略实现的。因此，二价氯化物络合物（BQA）PtCl（7）（BQA）PdCl（8）和（BQA）NiCl（9）均已制备并充分表征。对这三个复合物的每一个的
• Ligand survey results in identification of PNP pincer complexes of iridium as long-lived and chemoselective catalysts for dehydrogenative borylation of terminal alkynes
  作者：Chun-I Lee、Jessica C. DeMott、Christopher J. Pell、Alyson Christopher、Jia Zhou、Nattamai Bhuvanesh、Oleg V. Ozerov

  DOI：10.1039/c5sc02161h

  日期：——

  Following the report on the successful use of SiNN pincer complexes of iridium as catalysts for dehydrogenative borylation of terminal alkynes (DHBTA) to alkynylboronates, this work examined a wide variety of related pincer ligands in the supporting role in DHBTA. The ligand selection included both new and previously reported ligands and was developed to explore systematic changes to the SiNN framework

  继关于成功使用铱的 SiNN 钳形配合物作为末端炔烃 (DHBTA) 脱氢硼化为炔基硼酸盐的催化剂的报告之后，这项工作研究了各种相关钳形配体在 DHBTA 中的支持作用。配体选择包括新的和以前报道的配体，旨在探索 SiNN 框架（8-（2-二异丙基甲硅烷基苯基）氨基喹啉）的系统变化。令人惊讶的是，只有二芳基氨基/双（膦） PNP 系统显示出任何 DHBTA 反应性。筛选中使用的特定 PNP 配体（带有两个二异丙基膦基侧供体）显示 DHBTA 活性低于 SiNN。然而，利用 PNP 系统提供的配体优化机会，通过磷取代的变化导致发现了一种催化剂，其活性、寿命和范围远远超过了原始 SiNN 原型。在模型 PNP 系统中制备了几种 Ir 配合物，并作为催化循环中的潜在中间体进行了评估。其中，(PNP)Ir 二硼基络合物和硼基亚乙烯基络合物显示出催化能力较差，因此可能不是催化循环的一部分。
• Synthesis of Quinoline-Based NNN-Pincer Nickel(II) Complexes: A Robust and Improved Catalyst System for C–H Bond Alkylation of Azoles with Alkyl Halides
  作者：Ulhas N. Patel、Dilip K. Pandey、Rajesh G. Gonnade、Benudhar Punji

  DOI：10.1021/acs.organomet.6b00201

  日期：2016.6.13

  The quinoline-based pincer nickel(II) complexes kappa(N),kappa(N),kappa(N) -R2N-C6H4-(mu-N)-C9H6N}NiX (((NNNQ)-N-R2)NiCl: R = Me) 2a; R = Et, 2b) were synthesized by the reaction of the ligand precursors ((NNNQ)-N-R2)H (R = Me, 1a; R = Et, 1b) with (DME)NiCl2 in the presence of Et3N. Similarly, the pincer mickel(II) derivatives ((NNNQ)-N-R2)NiX (R = Me, X = Br, 3a; R = Et, X = Br, 3b; R = Me, X = OAc, 4a) were obtained by treatment of the ligands ((NNNQ)-N-R2)H with the nickel precursor (THF)(2)NiBr2 or Ni(QAc)(2). All of these complexes were characterized by H-1 and C-13 NMR spectroscopy as well as by elemental analysis. Further, the molecular structures of 2a and 3a,b were elucidated by X-ray crystallography. Complex 2a is found to be an efficient catalyst for the direct C-H bond alkylation of substituted benzothiazoles and oxazoles with various unactivated alkyl halides containing beta-hydrogens under mild reaction conditions. The catalyst 2a is very robust and was recycled and reused five times for the alkylation reaction without a decrease in its catalytic activity. Preliminary studies reveal that the catalyst 2a acts as an active catalyst and the alkylation reaction appears to operate via a radical pathway.