cis-N,N′-diphenylazodioxide | 115626-83-0

• 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: cis-N,N′-diphenylazodioxide
• 英文别名: nitrosobenzene dimer；(Z)-diphenyl-diazene-N,N'-dioxide；(Z)-Diphenyl-diazen-N,N'-dioxid；dimeres Nitrobenzol；cis-Nitrosobenzene dimer；(Z)-oxido-[oxido(phenyl)azaniumylidene]-phenylazanium
• CAS: 115626-83-0
• 化学式: C₁₂H₁₀N₂O₂
• 分子量: 214.224
• InChiKey: WHFNSVMCGRQIRC-YPKPFQOOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 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：
  57.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-N,N′-diphenylazodioxide 生成 亚硝基苯
  参考文献：
  名称：

  Fletcher, Daniel A.; Gowenlock, Brian G.; Orrell, Keith G., Journal of the Chemical Society. Perkin Transactions 2 (2001), 1998, # 4, p. 797 - 803

  摘要：

  DOI：
• 作为产物：
  描述：

  亚硝基苯 以 氘代氯仿 为溶剂， 生成 cis-N,N′-diphenylazodioxide
  参考文献：
  名称：

  亚硝基苯交叉二聚：溶液和固态的结构选择性

  摘要：

  摘要 亚硝基苯形成二聚分子结构（偶氮二氧化物）的可能性被用作溶液和固态分子间选择性研究的模型。通过变温 1H NMR、固态 NMR (CP MAS)、IR 和 ab initio 计算研究了对和间取代亚硝基苯对的不同组合的交叉二聚。很明显，对亚硝基苯具有非选择性，因为它与所有研究的亚硝基苯伙伴形成二聚体。相反，对甲氧基亚硝基苯在大多数情况下不会形成二聚体。可以通过晶格中分子排列的影响来解释溶液中形成二聚体的能力与固态不同的证据。

  DOI：

  10.1016/j.molstruc.2010.05.034

文献信息

• Study of the monomer-dimer equilibrium of nitrosobenzene using multinuclear one- and two-dimensional NMR techniques
  作者：Keith G. Orrell、Vladimir Šik、David Stephenson

  DOI：10.1002/mrc.1260251118

  日期：1987.11

  nitrosobenzene in CDCI3 solution was studied in the temperature range ‐50 to 30 °C using 13C, 15N and 17O NMR spectroscopy. Decreasing temperature favours the dimeric azodioxy species, and below ca 10 °C both cis and trans dimers were detected in addition to the monomer. The relative abundance of the trans dimer is low (⩽6%) at all temperatures and this is the first report of its existence in solution. The monomer

  使用 13C、15N 和 17O NMR 光谱在 -50 至 30°C 的温度范围内研究了亚硝基苯在 CDCI3 溶液中的单体-二聚体平衡。降低温度有利于二聚偶氮二氧基物种，并且在低于约 10°C 时，除了单体之外，还检测到顺式和反式二聚体。在所有温度下，反式二聚体的相对丰度都很低（⩽6%），这是它在溶液中存在的第一份报告。单体和二聚体物质的特征在于它们的 13C 和 15N 位移，它们之间的交换通过 13C 2D-EXSY 光谱定量测量。交换仅发生在顺式二聚体和单体之间以及反式二聚体和单体之间，活化能 ΔG≠(298.15 K) 分别为 65.8±0.1 和 70.0±0.3 kJ mol-1。
• Oxidation of aromatic amines with hydrogen peroxide catalyzed by cetylpyridinium heteropolyoxometalates
  作者：Sigeki Sakaue、Takashi Tsubakino、Yutaka Nishiyama、Yasutaka Ishii

  DOI：10.1021/jo00066a012

  日期：1993.7

  Various substituted anilines 1 were selectively converted into the corresponding nitrosobenzenes 2 or nitrobenzenes 3 by oxidation with aqueous hydrogen peroxide catalyzed by heteropolyoxometalates. The oxidations of anilines 1 with 35% H2O2 catalyzed by peroxotungstophosphate (PCWP) at room temperature in chloroform under two-phase conditions afforded nitrosobenzenes 2 with high selectivity. When the same reactions were carried out at higher temperature (e.g., refluxing chloroform), nitrobenzenes 3 were obtained in good yields. The oxidation of aniline (1a) with dilute H2O2 catalyzed by PCWP (2 wt %) in an aqueous medium produced azoxybenzene (4a) with high selectivity. Phenylazoxyalkanes 7 were prepared by the first direct cooxidation of la in the presence of primary aliphatic amines 6. For example, the oxidation of a 1:2 mixture of 1a and hexylamine (6b) with 35 % H2O2 (6 equiv) in the presence of PCWP produced phenylazoxyhexane (7b) (51 %) along with a small amount of 4a (8 %). The reaction path for the conversion of anilines to azoxy-, nitroso-, and nitrobenzenes is described.
• Azoulay, Michel; Fischer, Ernst, Journal of the Chemical Society. Perkin transactions II, 1982, p. 637 - 642
  作者：Azoulay, Michel、Fischer, Ernst

  DOI：——

  日期：——
• Photothermal Reactions of Nitrosobenzene and Halonitrosobenzenes in Solid-state
  作者：Anamarija Knežević、Tina Medančić、Srđan Milovac、Ivana Biljan、Ivan Halasz、Hrvoj Vančik

  DOI：10.5562/cca1714

  日期：——

  Photothermal reactions of the dimers of nitrosobenzene, m-chloronitrosobenzene, and p-chloronitrosobenzene were studied in solid-state by IR spectroscopy at low temperatures and by X-ray powder diffraction. It was found for the first time that photothermal cycle (photolytic dissociation followed by thermal dimerization) could successively be performed also with Z-configured dimeric nitrosobenzene.Halonitrosobenzenes dimers with E-configuration afforded different photo behavior depending on the position of halogen atom on the benzene ring: while m-halonitrosobenzenes do not dissociate under UV irradiation, p-chloronitrosobenzene, as well as previously studied p-bromonitrosobenzene photolyses very efficiently with recovering of the original crystal phase. Kinetics of thermal dimerization was measured in solid-state, and it was found that the reaction phase transformation occurs as a two-dimensional growth through the crystal. (doi: 10.5562/cca1714)