N-(2-nitrophenyl)hydroxylamine | 19613-87-7

• 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-(2-nitrophenyl)hydroxylamine
• 英文别名: 2-nitro-phenyl-hydroxylamine；N-hydroxy-2-nitrobenzamine；o-Nitrophenylhydroxylamin；N-(2-nitro-phenyl)-hydroxylamine；N-(2-Nitro-phenyl)-hydroxylamin；N-<2-Nitro-phenyl>-hydroxylamin；Hydroxylamine, N-(o-nitrophenyl)-
• CAS: 19613-87-7
• 化学式: C₆H₆N₂O₃
• 分子量: 154.125
• InChiKey: ADEHRJVMSGIOHI-UHFFFAOYSA-N

物化性质

• 熔点：
  68-70 °C
• 沸点：
  313.4±44.0 °C(Predicted)
• 密度：
  1.514±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  78.1
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-(2-nitrophenyl)hydroxylamine 以 吡啶 、 苯 为溶剂， 反应 24.5h， 生成 2,2'-dinitroazoxybenzene
  参考文献：
  名称：

  Bryant, Ian R.; Dyall, Leonard K., Australian Journal of Chemistry, 1989, vol. 42, # 12, p. 2275 - 2288

  摘要：

  DOI：
• 作为产物：
  描述：

  1,2-二硝基苯 在 2 % platinum on carbon 、 氢气 作用下， 以 四氢呋喃 为溶剂， 9.99 ℃ 、100.0 kPa 条件下， 反应 2.83h， 以91.9%的产率得到N-(2-nitrophenyl)hydroxylamine
  参考文献：
  名称：

  Carbon supported Pt colloid as effective catalyst for selective hydrogenation of nitroarenes to arylhydroxylamines

  摘要：

  负载于碳上的铂胶体是一种活性高且选择性强的催化剂，能将带有吸电子取代基的硝基芳香化合物部分氢化为相应的N-芳基羟胺，这表明了一种无添加剂的绿色催化方法，可用于芳基羟胺的合成。

  DOI：

  10.1039/b916686f

文献信息

• Mechanism and reactivity in perborate oxidation of anilines in acetic acid
  作者：Chockalingam Karunakaran、Ramasamy Kamalam

  DOI：10.1039/b208199g

  日期：2002.12.6

  Perborate but not percarbonate in acetic acid generates peracetic acid on standing and the peracetic acid oxidation of anilines is fast. The oxidation with a fresh solution of perborate in acetic acid is smooth and second order but the specific oxidation rate increases with increasing [perborate]0 or [boric acid]. Perborate on dissolution affords hydrogen peroxide and a borate; the latter assists the former in the oxidation. The oxidation rates of anilines under identical conditions do not conform to any of the linear free energy relationships but the reaction rates of molecular anilines do. Perborate oxidation proceeds via two reaction paths but the overall oxidation rates of molecular anilines conform to structure–reactivity relationships; the transition states do not differ significantly. Analysis of the oxidation rates of perborate and percarbonate reveals that while perborate oxidation is faster than percarbonate it is at least as selective as the latter.

  在乙酸中，过硼酸盐而非过碳酸盐静置时会产生过乙酸，而过乙酸对苯胺的氧化反应迅速。使用新鲜配制的乙酸过硼酸盐溶液进行氧化反应平稳且具有二级反应特性，但特定的氧化速率随[过硼酸盐]0或[硼酸]浓度的增加而增加。过硼酸盐溶解时产生过氧化氢和硼酸盐；后者在氧化过程中辅助前者。在相同条件下，苯胺的氧化速率不符合任何线性自由能关系，但分子苯胺的反应速率却符合。过硼酸盐氧化通过两条反应路径进行，但分子苯胺的整体氧化速率符合结构-反应活性关系；过渡态的差异不大。对过硼酸盐和过碳酸盐氧化速率的分析显示，尽管过硼酸盐的氧化速率更快，但其选择性至少不亚于过碳酸盐。
• A novel strategy for the preparation of arylhydroxylamines: chemoselective reduction of aromatic nitro compounds using bakers' yeast
  作者：Feng Li、Jingnan Cui、Xuhong Qian、Rong Zhang

  DOI：10.1039/b408566c

  日期：——

  Using bakers' yeast as a biocatalyst, the chemoselective reduction of aromatic nitro compounds bearing electron-withdrawing groups gave the corresponding hydroxylamines with good to excellent conversion under mild conditions.

  使用面包酵母作为生物催化剂，带有吸电子基团的芳香族硝基化合物的化学选择性还原在温和条件下得到了相应的羟胺，具有良好或优异的转化率。
• Green-light photocatalytic reduction using dye-sensitized TiO₂and transition metal nanoparticles
  作者：Stefan Füldner、Ralph Mild、Heiko Ingo Siegmund、Josef A. Schroeder、Michael Gruber、Burkhard König

  DOI：10.1039/b918140g

  日期：——

  Nitrobenzenes are cleanly reduced to anilines using Ru-sensitized TiO2 photocatalysts and green light irradiation, if very small amounts of transitions metal salts are added, which form metal nanoparticles of narrow size distribution under the experimental conditions. The catalyst system is prepared by simple mixing of the components and is therefore easy to apply in organic synthesis. As light sources, commercial high power LEDs or sunlight are used. We report the optimization of the reaction conditions, the effect of trace amounts of added metal salts and demonstrate the use of green light photoreduction in the conversion of several nitrobenzene derivatives.

  使用Ru敏化的TiO2光催化剂和绿色光照射，可以干净地将硝基苯还原为苯胺，条件是加入极少量的过渡金属盐，这些盐在实验条件下形成尺寸分布狭窄的金属纳米颗粒。该催化体系通过简单混合各组分制备，因此在有机合成中易于应用。光源可以使用商用高功率LED或太阳光。我们报告了反应条件的优化、微量添加金属盐的影响，并展示了绿色光光还原在几种硝基苯衍生物转化中的应用。
• Highly selective and controllable synthesis of arylhydroxylamines by the reduction of nitroarenes with an electron-withdrawing group using a new nitroreductase BaNTR1
  作者：Hieu-Huy Nguyen-Tran、Gao-Wei Zheng、Xu-Hong Qian、Jian-He Xu

  DOI：10.1039/c3cc48590k

  日期：——

  A new bacterial nitroreductase has been identified and used as a biocatalyst for the controllable reduction of a variety of nitroarenes with an electron-withdrawing group to the corresponding N-arylhydroxylamines under mild reaction conditions with excellent selectivity (>99%). This method therefore represents a green and efficient method for the synthesis of arylhydroxylamines.

  已鉴定出一种新的细菌硝基还原酶，并将其用作生物催化剂，用于在温和的反应条件下以优异的选择性（> 99％）将具有吸电子基团的各种硝基芳烃可控地还原为相应的N-芳基羟胺。因此，该方法代表了一种合成芳基羟胺的绿色有效方法。
• Effect of substituents on the rate of oxidation of anilines with peroxomonosulfate monoanion (HOOSO−3) in aqueous acetonitrile: A mechanistic study
  作者：Subbiah Meenakshisundaram、M. Selvaraju、N. M. Made Gowda、Kanchugarakoppal S. Rangappa

  DOI：10.1002/kin.20119

  日期：2005.11

  Mechanistic studies on the oxidation of 18 meta-, para-, and ortho-substituted anilines (Ans) by HOOSO−3 in aqueous acetonitrile medium have been performed. The reaction can be characterized by the experimental rate equation, The addition of p-toluenesulfonic acid (TsOH) retards the reaction. The increase in the reactivity of anilines as the medium is made more aqueous is interpreted. The reaction

  已经对 HOOSO-3 在水性乙腈介质中氧化 18 种间位、对位和邻位取代的苯胺 (Ans) 进行了机理研究。该反应可以通过实验速率方程来表征，对甲苯磺酸（TsOH）的加入延缓了反应。解释了随着介质变得更含水，苯胺的反应性增加。与胺对过硫酸盐氧的限速亲核攻击相一致的系列中的胺上的给电子基团增强了反应。所提出的机理涉及快速将苯基羟胺转化为亚硝基苯。ESR 研究表明反应中不存在自由基。已经进行了各种尝试来根据 LFER 图分析实验速率常数。使用 σ- 值和 Yukawa-Tsuno 方程的 σ- 形式获得了改进的相关性。© 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 649–657, 2005