4-(2,4-diaminophenyl)iminocyclohexa-2,5-dien-1-one | 24093-23-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-(2,4-diaminophenyl)iminocyclohexa-2,5-dien-1-one
• 英文别名: N¹--2-amino-p-benzochinon-diimin；N¹-(p-Hydroxy-phenyl)-2-amino-p-benzochinon-diimin
• CAS: 24093-23-0
• 化学式: C₁₂H₁₁N₃O
• 分子量: 213.239
• InChiKey: IDIMPGXMVWFIEJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  82.46
• 氢给体数：
  3.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  对氨基苯酚 在 氧气 作用下， 以 aq. buffer 为溶剂， 反应 3.5h， 生成 4-(2,4-diaminophenyl)iminocyclohexa-2,5-dien-1-one
  参考文献：
  名称：

  Molecular-Level Insight into the Differential Oxidase and Oxygenase Reactivities of de Novo Due Ferri Proteins

  摘要：

  Using the single-chain due ferri (DFsc) peptide scaffold, the differential oxidase and oxygenase reactivities of two 4A -> 4G variants, one with two histidines at the diiron center (G4DFsc) and the other with three histidines (3His-G4DFsc(Mut3)), are explored. By controlling the reaction conditions, the active form responsible for 4-aminophenol (4-AP) oxidase activity in both G4DFsc and 3His-G4DFsc(Mut3) is determined to be the substrate-bound biferrous site. Using circular dichroism (CD), magnetic CD (MCD), and variable-temperature, variable-field (VTVH) MCD spectroscopies, 4-AP is found to bind directly to the biferrous sites of the DF proteins. In G4DFsc, 4-AP increases the coordination of the biferrous site, while in 3His-G4DFsc(Mut3), the coordination number remains the same and the substrate likely replaces the additional bound histidine. This substrate binding enables a two-electron process where 4-AP is oxidized to benzoquinone imine and O-2 is reduced to H2O2. In contrast, only the biferrous 3His variant is found to be active in the oxygenation of p-anisidine to 4-nitroso-methoxybenzene. From CD, MCD, and VTVH MCD, p-anisidine addition is found to minimally perturb the biferrous centers of both G4DFsc and 3His-G4DFsc(Mut3), indicating that this substrate binds near the biferrous site. In 3His-G4DFsc(Mut3), the coordinative saturation of one iron leads to the two-electron reduction of O-2 at the second iron to generate an end-on hydroperoxo-Fe(III) active oxygenating species.

  DOI：

  10.1021/jacs.5b03524

文献信息

• Benzoquinone imines. Part 18. Kinetics and mechanism of oxidative coupling reactions involving N,N-bis-(2-hydroxyethyl)-p-phenylenediamine
  作者：David J. Palling、Keith C. Brown、John F. Corbett

  DOI：10.1039/p29860000065

  日期：——

  A kinetic and mechanistic study of oxidative coupling reactions of N,N-bis-(2-hydroxyethyl)-p-phenylenediamine with m-phenylenediamines, phenols, and acetoacetanilide is described. The reactions involve the rapid establishment of an equilibrium between N,N-bis-(2-hydroxyethyl)-p-benzoquinone di-imine and a hydroxy-amine intermediate (3). Competition between direct coupling of N,N-bis-(2-hydroxyethyl)-p-benzoquinone

  的氧化偶联反应的动力学和机理研究Ñ，ñ -双- （2-羟乙基） - p苯二胺与米苯二胺类，酚类，乙酰乙酰苯胺和描述。反应包括在N，N-双-（2-羟乙基）-对苯醌二亚胺和羟胺中间体（3）之间快速建立平衡。N，N-双-（2-羟乙基）-对苯醌二亚胺的直接偶联与经由（3）水解为对苯醌单胺之间的竞争）和随后的偶联会导致两种染料产物的混合物。相对产率取决于pH和偶合剂浓度。提供了形成中间体（3）的动力学证据。
• A De Novo Heterodimeric Due Ferri Protein Minimizes the Release of Reactive Intermediates in Dioxygen-Dependent Oxidation
  作者：Marco Chino、Linda Leone、Ornella Maglio、Daniele D'Alonzo、Fabio Pirro、Vincenzo Pavone、Flavia Nastri、Angela Lombardi

  DOI：10.1002/anie.201707637

  日期：2017.12.4

  Not just a four-helix bundle: The use of a diiron-binding four-helix bundle scaffold with an asymmetric active site leads to an enhancement in selectivity of the iron-catalyzed oxidative coupling of phenols. The stabilization of the oxidized intermediate in the binding pocket enables the net four-electron O2 reduction, without release of any detectable H2O2.

  不仅是四螺旋束：具有不对称活性位点的二铁结合四螺旋束支架的使用会导致铁催化的酚氧化偶联的选择性增强。结合口袋中被氧化的中间体的稳定化使得四电子O 2净减少，而不会释放任何可检测的H 2 O 2。