N,N-dimethyl-4-[15N]nitroso-aniline | 81201-22-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N,N-dimethyl-4-[15N]nitroso-aniline
• 英文别名: 4-dimethylamino-¹⁵N-nitrosobenzene；N,N-dimethyl-4-[¹⁵N]nitroso-aniline
• CAS: 81201-22-1
• 化学式: C₈H₁₀N₂O
• 分子量: 151.173
• InChiKey: CMEWLCATCRTSGF-QBZHADDCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.15
• 重原子数：
  11.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  32.67
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  N,N-dimethyl-4-[15N]nitroso-aniline 在 palladium on activated charcoal sodium tetrahydroborate 作用下， 生成 N,N-dimethyl-benzene-1,4-[N'-¹⁵N]diamine
  参考文献：
  名称：

  Solvent and Solvent Density Effects on the Spectral Shifts and the Bandwidths of the Absorption and the Resonance Raman Spectra of Phenol Blue

  摘要：

  We have measured the absorption and the resonance Raman spectra of a solvatochromic dye, phenol blue, in liquid and supercritical solvents. We have found anomalous solvent dependence of the absorption bandwidth in liquid solvents: the width has apparently no correlation with the absorption peak shift. On the other hand, we have found good linear correlation between the absorption peak shift and the peak position of the resonance Raman bands (the C=N and the C=O stretching modes). The relative intensities of the Raman bands and the bandwidth of the C=N stretching mode also show correlation with the absorption peak shift. Incorporating these Raman data, the anomalous bandwidth of the absorption spectrum is explained by the change of the intramolecular vibrational contribution to the absorption bandwidth due to the electronic structure change by the solvent, which cancels the change of the solvent contribution. We have estimated the solvent reorganization energy assuming linear dependence of the intramolecular contribution on the absorption band center and neglecting the solvent reorganization energy in alkanes such as ethane and cyclohexane. In liquid solution, the estimated solvent reorganization energy is correlated fairly well with the absorption peak shift. Solvent dependence of the Raman bandwidth of the C=N stretching mode resembles the solvent dependence of the solvent reorganization energy estimated in this way. Relatively large bandwidths of both absorption and resonance Raman spectra have been observed in supercritical solvents compared with those in liquid solvents of a similar absorption peak shift. We interpreted this as due to the small refractive indices of the supercritical solvents relative to the liquid solvents; the large refractive indices of the liquid solvents only make the absorption peak shifts without broadening the absorption spectra.

  DOI：

  10.1021/jp971310f
• 作为产物：
  描述：

  N,N-二甲基苯胺 在 盐酸 、 亚硝酸钠-15N 作用下， 以 水 为溶剂， 反应 1.25h， 生成 N,N-dimethyl-4-[15N]nitroso-aniline
  参考文献：
  名称：

  调节一系列铜/亚硝基芳烃加合物中的球形电子转移。

  摘要：

  创建了一系列铜/亚硝基芳烃配合物，它们模仿了仿生O 2通过铜（I）活化的几个步骤。N，N，N '，N的铜（I）配合物的反应'-四甲基丙烯二胺与一系列对位取代的亚硝基苯衍生物会导致加成反应，其中亚硝基芳烃（ArNO）分别被零价，一个或两个电子还原，分别类似于二价氧，超氧化物和过氧化物。这些加合物的几何和电子结构通过X射线衍射，振动分析，紫外可见光谱，NMR，电化学和密度泛函理论（DFT）计算来表征。的NO部分的键合方式依赖于ARNO部分的氧化态：κN为阿诺，单核η 2 -NO和双核μ-η 2：η 1为ARNO • - ，和双核μ-η 2：η 2为ArNO2 –。15个通过测量NO伸缩频率（N同位素标记确认减速状态1392厘米-1为κN-阿诺，1226厘米-1为η 2 -ArNO • -，1133厘米-1为双核μ-η 2：η 1 -阿诺• - ，和875厘米-1为双核μ-η 2：η 2为ARNO

  DOI：

  10.1021/acs.inorgchem.9b03175

文献信息

• The first structural studies of nitrosoarene binding to iron-(II) and -(III) porphyrins
  作者：Li-Sheng Wang、Li Chen、Masood A. Khan、George B. Richter-Addo

  DOI：10.1039/cc9960000323

  日期：——

  The nitrosoarene ligands in ferrous [FeII(tpp)(PhNO)2] are bound through their nitrogen atoms, whereas they are bound through their oxygen atoms in ferric [FeIII(tpp)(Et2NC6H4NO)2]SbF6.

  亚铁[FeII(tpp)(PhNO)2]中的亚硝基烯配体是通过氮原子结合的，而在铁[FeIII(tpp)(Et2NC6H4NO)2]SbF6 中则是通过氧原子结合的。
• Insight into the preferential N-binding <i>versus</i> O-binding of nitrosoarenes to ferrous and ferric heme centers
  作者：Erwin G. Abucayon、Jia-Min Chu、Megan Ayala、Rahul L. Khade、Yong Zhang、George B. Richter-Addo

  DOI：10.1039/d0dt03604h

  日期：——

  crystallography and density functional theory (DFT) analyses of new representative ferrous and ferric ArNO compounds to provide the first theoretical insight into preferential N-binding versus O-binding of ArNOs to hemes. Our X-ray structural results favored N-binding of ArNO to ferrous heme centers, and O-binding to ferric hemes. Results of the DFT calculations rationalize this preferential binding on

  亚硝基芳烃 (ArNO) 是有毒的代谢中间体，可与血红素蛋白结合以抑制其功能。尽管它们的许多生物学功能涉及与血红素的 Fe 中心的配位，但决定这些 ArNO 的 N 结合或 O 结合的因素尚未确定。我们利用 X 射线晶体学和密度泛函理论 (DFT) 对新的代表性亚铁和三价 ArNO 化合物进行分析，为 ArNO 与血红素的优先 N 结合与O 结合提供了第一个理论见解。我们的 X 射线结构结果有利于 ArNO 与亚铁血红素中心的 N 结合，以及与铁血红素中心的 O 结合。 DFT 计算结果根据相关自旋态的能量合理化了这种优先结合，并揭示了观察到的亚铁 N 配位和铁 O 配位中的主要稳定力是 dπ–pπ* 和 dσ–pπ* ， 分别。我们的结果首次解释了为什么亚铁-ArNO化合物原位氧化为其三价铁态会导致观察到的配体随后解离。