N,N'-(4,5-dimethyl-1,2-phenylene)dipicolinamide | 216389-76-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N,N'-(4,5-dimethyl-1,2-phenylene)dipicolinamide
• 英文别名: N,N’-(4,5-dimethyl-1,2-phenylene)dipicolinamide；1,2-bis(pyridine-2-carboxamido)-4,5-dimethylbenzene；N,N'-bispyridinecarboxamide-4,5-dimethylbenzenediamine；H2Me2bpb；N-[4,5-dimethyl-2-(pyridine-2-carbonylamino)phenyl]pyridine-2-carboxamide
• CAS: 216389-76-3
• 化学式: C₂₀H₁₈N₄O₂
• 分子量: 346.389
• InChiKey: MBFOPULWZFFYPG-UHFFFAOYSA-N

物化性质

• 沸点：
  411.2±45.0 °C(Predicted)
• 密度：
  1.301±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  84
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  copper(II) perchlorate hexahydrate 、 N,N'-(4,5-dimethyl-1,2-phenylene)dipicolinamide 以 甲醇 为溶剂， 以65%的产率得到Cu(1,2-bis(pyridine-2-carboxamido)-4,5-dimethylbenzene-2H)
  参考文献：
  名称：

  Steric effect on construction of Cu(II) complexes with pyridine carboxamide ligands

  摘要：

  The structures of three new Cu(II) complexes with pyridine carboxamide ligands (Me(2)bpb, 6-Me-2-Mebpb, and 6-Me-2-Me(2)bpb) have been determined. 6-Methyl-substituted pyridyl bpb ligands produced dimeric compounds with Cu(II) ions, and weak interactions between dimers can make even polymeric compounds, while bpb ligands without 6-methyl substitution produced monomeric Cu(II) complexes. The large distortion effects of 6-methyl-substitution are shown in Cu(II) complexes with 6-methyl-substituted pyridyl bpb ligands. This result suggests that the steric effect of 6-methyl-substitution plays important role for distortion of the structure, and 6-methyl-substitution can also influence to make polymeric compounds with interactions between Cu(II) ions and neighbor carbonyl oxygen atoms. In addition, the voltammetric behaviors of the Cu complexes were examined and classified into two groups, with/without 6-methyl group. The complexes without 6-methyl group show reversible redox waves at similar to-1.6 V, and the complexes with 6-methyl group do irreversible redox ones at similar to-1.3 V, indicating that the presence of the methyl group of 6-position of the complex makes the reduction of the complexes easier. (C) 2007 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molstruc.2007.10.006
• 作为产物：
  描述：

  2-吡啶甲酸 、 4，5-二甲基-1，2-苯二胺 在 亚磷酸三苯酯 作用下， 以 吡啶 为溶剂， 反应 4.0h， 以78%的产率得到N,N'-(4,5-dimethyl-1,2-phenylene)dipicolinamide
  参考文献：
  名称：

  New cobalt, iron and chromium catalysts based on easy-to-handle N₄-chelating ligands for the coupling reaction of epoxides with CO₂

  摘要：

  在本篇论文中，我们报道了基于取代的N4-N,N-双(2-吡啶羧酰胺)-1,2-苯配体的多种过渡金属配合物在环氧烷与二氧化碳的偶联反应中的催化应用。这些配合物在环己烯氧化物和丙烯氧化物的反应中得到了测试。此外，我们还评估了该催化体系的循环使用性，并对选定的催化剂进行了一系列商业上可获得的环氧烷的大范围催化筛选。

  DOI：

  10.1039/c3dt53084a

文献信息

• Photolabile Ruthenium Nitrosyls with Planar Dicarboxamide Tetradentate N₄ Ligands:  Effects of In-Plane and Axial Ligand Strength on NO Release
  作者：Apurba K. Patra、Michael J. Rose、Karen A. Murphy、Marilyn M. Olmstead、Pradip K. Mascharak

  DOI：10.1021/ic040030t

  日期：2004.7.1

  and characterized by spectroscopy and X-ray diffraction analysis. All four complexes exhibit nu(NO) in the range 1830-1870 cm(-)(1) indicating the [Ru-NO](6) configuration. Clean (1)H NMR spectra in CD(3)CN (or (CD(3))(2)SO) confirm the S = 0 ground state for all four complexes. Although the complexes are thermally stable, they release NO upon illumination. Rapid NO dissociation occurs when solutions

  四个钌亚硝酰基，即[（bpb）Ru（NO）（Cl）]（1），[（Me（2）bpb）Ru（NO）（Cl）]（2），[（Me（2）bpb）Ru （NO）（py）]（BF（4））（3）和[（Me（2）bqb）Ru（NO）（Cl）]（4）（H（2）bpb = 1,2-bis（吡啶-2-甲酰胺基）苯，H（2）Me（2）bpb = 1,2-双（吡啶-2-甲酰胺基）-4,5-二甲基苯，H（2）Me（2）bqb = 1,2 -双（奎那丁-2-甲酰胺基）-4,5-二甲基苯； H是可分解的酰胺质子），已通过光谱法和X射线衍射分析进行了表征。所有四个复合物均在1830-1870 cm（-）（1）范围内显示nu（NO），表明[Ru-NO]（6）构型。CD（3）CN（或（CD（3））（2）SO）中的干净的（1）H NMR光谱确认所有四个络合物的S = 0基态。尽管配合物是热稳定的，但它们在光照下不会释放NO。当1-
• Structural and spectroscopic evidence for linkage isomerism of bound nitrite in a {Fe–NO}6 nitrosyl derived from a tetradentate dicarboxamide ligand: More parallels between heme and non-heme systems
  作者：Michael J. Rose、Apurba K. Patra、Marilyn M. Olmstead、Pradip K. Mascharak

  DOI：10.1016/j.ica.2010.04.023

  日期：2010.10

  Abstract The ambidentate ligand nitrite (NO2) binds to transition metal centers through the N (nitro) or O (nitrito) atom. In metal porphyrin complexes, the energy difference between the two linkage isomers is small and hence slight differences in reaction conditions and/or ligand design give rise to formation of the isomers in different ratios. In the present work, similar behavior has been observed

  摘要环型配体亚硝酸盐（NO2）通过N（硝基）或O（硝化）原子与过渡金属中心结合。在金属卟啉配合物中，两种键合异构体之间的能量差很小，因此反应条件和/或配体设计的细微差异导致以不同比例形成异构体。在本工作中，从非血红素平面二羧酰胺配体N，N'衍生的Fe–NO} 6亚硝酰基[（Me2bpb）Fe（NO）（NO2）]（2），也观察到了类似的行为。 -双吡啶甲酰胺-4,5-二甲基苯二胺（H2Me2bpb）。在厌氧条件下，Fe（III）络合物[（Me2bpb）Fe（py）2] ClO4（1）与MeCN中的NO（g）反应得到2，该产物同时含有N和O结合的异构体取决于反应条件的不同比例。在质子溶剂中 同样的反应得到Fe–NO} 7亚硝酰基[（Me2bpb）Fe（NO）]（3）。两种亚硝酰基均已通过红外光谱和X射线衍射研究进行了表征。
• High catalytic activities in the norbornene polymerization with neutral palladium complexes containing N4-type tetradentate chelating ligands
  作者：Dong-Hwan Lee、Jung Hwan Lee、Byeong Kwon Park、Eun Young Kim、Youngmee Kim、Cheal Kim、Ik-Mo Lee

  DOI：10.1016/j.ica.2009.08.026

  日期：2009.11

  polymerization catalyzed by new Pd(II) complexes bearing N4-type tetradentate ligands obtained from the reaction between a 6-methyl-2-picolinic acid or picolinic acid and appropriate diamines has been studied. A class of new palladium complexes, [Pd(X1X2bpb)] and [Pd(X1X2-6-Me2bpb)] (X1 = Me, X2 = Me (1 and 4); X1 = H, X2 = H (2 and 5); X1 = H, X2 = NO2 (3 and 6); bpb = N,N′-(o-phenylene)bis(pyridine-2-carboxamidate);

  摘要研究了由6-甲基-2-吡啶甲酸或吡啶甲酸与适当的二胺反应制得的带有N4-型四齿配体的新型Pd（II）配合物催化的降冰片烯聚合反应。一类新的钯配合物[Pd（X1X2bpb）]和[Pd（X1X2-6-Me2bpb）]（X1 = Me，X2 = Me（1和4）; X1 = H，X2 = H（2和5） ； X1 = H，X2 = NO2（3和6）； bpb = N，N'-（邻亚苯基）双（吡啶-2-甲酰胺基）; 6-Me2bpb = N，N'-（邻亚苯基）双合成并表征了（6-甲基吡啶-2-甲酰胺）。通过X射线晶体学测定Pd配合物5的分子结构，显示出扭曲的正方形平面构型。使用改性的甲基铝氧烷（MMAO）作为活化剂，钯配合物对降冰片烯的聚合表现出高催化活性。
• Novel Metallomacrocyclic Carboxamide Mn(II) Complexes as Efficient Catalysts for the Transfer Hydrogenation of Ketones
  作者：Robert T. Kumah、Francis K. Migwi、Markus Schmitz、Werner R. Thiel、Stephen O. Ojwach

  DOI：10.1002/cctc.202300971

  日期：2023.12.7

  Mn(II) complexes based on carboxamide ligands form efficient catalysts in the transfer hydrogenation of a wide scope of ketone substrates at very low catalyst concentrations. The current Mn(II) catalysts are relatively stable and affordable, thus offer superior alternatives to the more established Mn(I) carbonyl complexes in the transfer hydrogenation reactions.

  基于甲酰胺配体的双核 Mn(II) 配合物可在极低的催化剂浓度下，在多种酮底物的转移氢化反应中形成高效的催化剂。目前的 Mn(II) 催化剂相对稳定且价格实惠，因此为转移氢化反应中更成熟的 Mn(I) 羰基配合物提供了更好的替代品。
• Synthesis, crystal structure and electrochemistry of cobalt(III) carboxamide complexes with amine and azide ancillary ligands
  作者：Soraia Meghdadi、Kurt Mereiter、Mehdi Amirnasr、Fatemeh Karimi、Ahmad Amiri

  DOI：10.1016/j.poly.2013.09.032

  日期：2014.1

  Six cobalt(III) complexes of the type [Co-III(Me(2)bpb)(amine)(N-3)] (Me(2)bpb(2-) = N,N'-(4,5-dimethyl-1,2-phenylene)dipicolinamide and amine = piperidine (pprdn) (I), pyrrolidine (prldn) (2), morpholine (mrpln) (3), pyridine (py) (4), 4-methylpyridine(4-Mepy) (5) and 4-acetylpyridine (4-Acpy) (6)) have been synthesized and characterized by elemental analyses, IR and UV-Vis spectroscopy. The structures of 1,3 and 4 have been determined by X-ray crystallography. Me(2)bpb(2-) is a dianionic tetradentate ligand, furnishing a N4 set, such that two N atoms of the two pyridine rings and two amido N atoms occupy four equatorial positions. The amine and azide ligands occupy the two axial positions, leading to a distorted octahedral geometry around the central cobalt ion. The electrochemical behavior of these complexes in DMF solution indicates that partial solvolysis of the complexes occurs and the axial amine ligand is replaced by DMF solvent in 1-6 leading to a [Co-III(Me(2)bpb)(DMF)(N-3)] species. The two additional redox processes observed in the cyclic voltammograms of these complexes originate from the oxidation of the 4,5-dimethylorthophenylene moiety of the Me(2)bpb(2-) ligand and a Co-III/II redox process in [Co-III(Me2- bpb)(DMF)(N-3)I. The Co-III/II redox potential of the [Co-III(Me(2)bpb)(amine)(N-3)] complexes is influenced by the nature of the axial amine ligand and varies from -0.53 for 4-Acpy to -0.79 V for pyrrolidine. (C) 2013 Elsevier Ltd. All rights reserved.