N-phenyl-2-(pyridin-2-yl)diazenecarboxamide | 219809-91-3

• 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-phenyl-2-(pyridin-2-yl)diazenecarboxamide
• 英文别名: n1-Phenyl-n2-(2-pyridinyl)diazenecarboxamide；1-phenyl-3-pyridin-2-yliminourea
• CAS: 219809-91-3
• 化学式: C₁₂H₁₀N₄O
• 分子量: 226.238
• InChiKey: IHFPNTITRJDDEC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  66.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ammonium hexafluorophosphate 、 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 、 N-phenyl-2-(pyridin-2-yl)diazenecarboxamide 以 乙腈 为溶剂， 反应 19.5h， 以72%的产率得到
  参考文献：
  名称：

  钌偶氮羧酰胺半三明治复合物：配位模式对无碱转移加氢催化电子结构和活性的影响

  摘要：

  Azocarboxamides were used as chelating ligands in ruthenium half-sandwich complexes. The synthesis and characterization of two new complexes with an unprecedented coordination motif are presented together with an in-depth investigation of two recently published complexes. Three different coordination modes of the ligands were realized, as evident by NMR spectroscopy and single-crystal X-ray diffraction. The use of base during the synthesis leads to a coordination of a deprotonated ligand, while the introduction of additional donor atoms results in a noncoordinated amide group. The first systematic experimental (cyclic voltammetry and UV-vis-NIR and EPR spectroelectrochemistry) and theoretical (DFT) investigation of the electronic structure of metal complexes bearing this redox-active ligand class is presented, revealing redox processes with ligand contribution. The absorption spectra and electrochemistry are mainly determined by the protonation state of the ligand. While complexes 2[PF6], 3[PF6], and 4[PF6] with neutral azocarboxamides show similar electronic spectra and cyclovoltammograms, the incorporation of a deprotonated monoanionic ligand in complex 1 leads to significant changes of these properties. In contrast, the catalytic activity in the base-free transfer hydrogenation reaction is mainly dependent on the coordination of the amide group, with only minor effects of the protonation state. While complexes 3[PF6] and 4[PF6], with an uncoordinated amide group, are inactive without the addition of base, complexes 1 and 2[PF6], with a metal-bound amide group, show activity under base-free conditions. The impact of the position of the amide group together with the detection of metal hydride species in H-1 NMR spectroscopy suggests the operation of metal ligand bifunctional catalysis to take place when no base is added.

  DOI：

  10.1021/acs.organomet.6b00424
• 作为产物：
  描述：

  1-α-pyridylamino-3 phenyl-2 urea 在 ammonium cerium (IV) nitrate 作用下， 以 甲醇 为溶剂， 以72%的产率得到N-phenyl-2-(pyridin-2-yl)diazenecarboxamide
  参考文献：
  名称：

  Biological evaluation of diazene derivatives as anti-tubercular compounds

  摘要：

  Despite efforts made in chemotherapeutic research in the past and present, Mycobacterium tuberculosis (M.tb), the etiological agent of tuberculosis, still causes more than a million deadly casualties each year, second only to HIV. The rapid generation and spread of drug resistant strains, a problem exacerbated by co-infection with HIV demands further efforts in the investigation of novel classes of anti-tubercular compounds. A library of eight substituted diazenecarboxamides, three carbamoyldiazenecarboxylates and four diazene-1,2-dicarboxamides was synthesized in a straightforward manner followed by a biological evaluation of the compounds. We observed minimal inhibitory concentrations below 10 mu g/mL against the H37Rv lab strain of M.tb. Three compounds that showed a potency of 90% growth inhibition of M.tb at a concentration lower than 10 mu g/mL were further evaluated and showed potency against other clinically relevant mycobacterial species such as Mycobacterium bovis, Mycobacterium avium and Mycobacterium ulcerans. The selected compounds were examined for acute cell toxicity on a murine macrophage like monocyte cell line J774 A.1 in which the cell viability was reduced by 50% at concentrations ranging from 7.4 mu g/mL to 20.7 mu g/mL. Neither of the three compounds showed signs of genotoxicity by VITOTOX or by Comet assay. The study was complemented by demonstration of the inhibition of intracellular replication of M.tb H37Rv inside J774 A.1 cells at 2 mu g/mL concentration and the susceptibility of a MDR LAM-1 strain at concentrations between 5 and 1 mu g/mL of the most active compound. (C) 2014 Elsevier Masson SAS. All rights reserved.

  DOI：

  10.1016/j.ejmech.2013.12.057

文献信息

• Versatile Coordination of Azocarboxamides: Redox‐Triggered Change of the Chelating Binding Pocket in Ruthenium Complexes
  作者：Johannes Klein、Julia Beerhues、David Schweinfurth、Margarethe van der Meer、Martin Gazvoda、Goutam Kumar Lahiri、Janez Košmrlj、Biprajit Sarkar

  DOI：10.1002/chem.201803606

  日期：2018.12.5

  place among azo ligands owing to their versatility for metal coordination. Herein ruthenium complexes with two different azocarboxamide ligands that differ in the presence (or not) of a coordinating pyridyl heterocycle are presented. By making full use of the O,N(amide), N(azo), and N(pyridyl) coordinating sites, the first diruthenium complex that is bridged by an azo ligand containing two different binding

  偶氮羧酰胺由于其金属配位的多功能性而在偶氮配体中占有特殊的位置。本文提出了具有两个不同的偶氮羧酰胺配体的钌配合物，它们在配位的吡啶基杂环的存在（或不存在）方面不同。通过充分利用O，N（酰胺），N（偶氮）和N（吡啶基）配位位点，获得了第一个被包含两个不同结合口袋的偶氮配体桥接的二钌络合物。此外，已最终证明，在单核络合物中，钌中心的氧化导致螯合结合口袋处配位的完全改变。通过NMR光谱，质谱和单晶X射线衍射对络合物进行表征。此外，通过电化学，UV / Vis / NIR / EPR光谱电化学和DFT计算的组合，研究了螯合结合口袋中上述氧化还原触发变化的机理以及所有配合物的电子结构。这是首次在钌络合物以及偶氮基配体中观察到完整螯合结合口袋中氧化还原驱动的变化。因此，这些结果表明，这些通用的偶氮羧酰胺配体有可能用作氧化还原驱动的开关，可能与电催化有关。这是首次在钌络合物以及偶氮基配体中观察到完整螯合
• Biological evaluation of diazene derivatives as anti-tubercular compounds
  作者：Davie Cappoen、Vita Majce、Cynthia Uythethofken、Damijana Urankar、Vanessa Mathys、Marijan Kočevar、Luc Verschaeve、Slovenko Polanc、Kris Huygen、Janez Košmrlj

  DOI：10.1016/j.ejmech.2013.12.057

  日期：2014.3

  Despite efforts made in chemotherapeutic research in the past and present, Mycobacterium tuberculosis (M.tb), the etiological agent of tuberculosis, still causes more than a million deadly casualties each year, second only to HIV. The rapid generation and spread of drug resistant strains, a problem exacerbated by co-infection with HIV demands further efforts in the investigation of novel classes of anti-tubercular compounds. A library of eight substituted diazenecarboxamides, three carbamoyldiazenecarboxylates and four diazene-1,2-dicarboxamides was synthesized in a straightforward manner followed by a biological evaluation of the compounds. We observed minimal inhibitory concentrations below 10 mu g/mL against the H37Rv lab strain of M.tb. Three compounds that showed a potency of 90% growth inhibition of M.tb at a concentration lower than 10 mu g/mL were further evaluated and showed potency against other clinically relevant mycobacterial species such as Mycobacterium bovis, Mycobacterium avium and Mycobacterium ulcerans. The selected compounds were examined for acute cell toxicity on a murine macrophage like monocyte cell line J774 A.1 in which the cell viability was reduced by 50% at concentrations ranging from 7.4 mu g/mL to 20.7 mu g/mL. Neither of the three compounds showed signs of genotoxicity by VITOTOX or by Comet assay. The study was complemented by demonstration of the inhibition of intracellular replication of M.tb H37Rv inside J774 A.1 cells at 2 mu g/mL concentration and the susceptibility of a MDR LAM-1 strain at concentrations between 5 and 1 mu g/mL of the most active compound. (C) 2014 Elsevier Masson SAS. All rights reserved.
• Ruthenium Azocarboxamide Half-Sandwich Complexes: Influence of the Coordination Mode on the Electronic Structure and Activity in Base-Free Transfer Hydrogenation Catalysis
  作者：Michael G. Sommer、Sofiya Marinova、Michael J. Krafft、Damijana Urankar、David Schweinfurth、Martina Bubrin、Janez Košmrlj、Biprajit Sarkar

  DOI：10.1021/acs.organomet.6b00424

  日期：2016.9.12

  Azocarboxamides were used as chelating ligands in ruthenium half-sandwich complexes. The synthesis and characterization of two new complexes with an unprecedented coordination motif are presented together with an in-depth investigation of two recently published complexes. Three different coordination modes of the ligands were realized, as evident by NMR spectroscopy and single-crystal X-ray diffraction. The use of base during the synthesis leads to a coordination of a deprotonated ligand, while the introduction of additional donor atoms results in a noncoordinated amide group. The first systematic experimental (cyclic voltammetry and UV-vis-NIR and EPR spectroelectrochemistry) and theoretical (DFT) investigation of the electronic structure of metal complexes bearing this redox-active ligand class is presented, revealing redox processes with ligand contribution. The absorption spectra and electrochemistry are mainly determined by the protonation state of the ligand. While complexes 2[PF6], 3[PF6], and 4[PF6] with neutral azocarboxamides show similar electronic spectra and cyclovoltammograms, the incorporation of a deprotonated monoanionic ligand in complex 1 leads to significant changes of these properties. In contrast, the catalytic activity in the base-free transfer hydrogenation reaction is mainly dependent on the coordination of the amide group, with only minor effects of the protonation state. While complexes 3[PF6] and 4[PF6], with an uncoordinated amide group, are inactive without the addition of base, complexes 1 and 2[PF6], with a metal-bound amide group, show activity under base-free conditions. The impact of the position of the amide group together with the detection of metal hydride species in H-1 NMR spectroscopy suggests the operation of metal ligand bifunctional catalysis to take place when no base is added.