N-(3-硝基苯基)羟胺 | 6418-00-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: N-(3-硝基苯基)羟胺
• 英文名称: N-(3-nitrophenyl)hydroxylamine
• 英文别名: N-(3-nitrophenyl) hydroxylamine；N-(3-nitrophenyl)-hydroxylamine；m-Nitrophenylhydroxylamin；N-(3-nitro-phenyl)-hydroxylamine；N-(3-Nitro-phenyl)-hydroxylamin；N-(m-nitrophenyl) hydroxylamine；Benzenamine, N-hydroxy-3-nitro-
• CAS: 6418-00-4
• 化学式: C₆H₆N₂O₃
• 分子量: 154.125
• InChiKey: VSPZSXLLFMWWLY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 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-(3-硝基苯基)羟胺 在 potassium dichromate 、 乙醇 、 硫酸 作用下， 生成 3,3'-dinitro azoxybenzene
  参考文献：
  名称：

  Brand; Mahr, Journal fur praktische Chemie (Leipzig 1954), 1931, vol. <2>131, p. 97,119

  摘要：

  DOI：
• 作为产物：
  描述：

  1,3-二硝基苯 在 一水合肼 作用下， 反应 0.08h， 以94%的产率得到N-(3-硝基苯基)羟胺
  参考文献：
  名称：

  聚苯乙烯稳定的铱纳米粒子催化硝基芳烃化学和区域选择性半氢化成 N-芳基羟胺

  摘要：

  聚苯乙烯稳定的铱 (Ir@PS) 纳米粒子 (NPs) 作为多相催化剂已被开发并通过 IR、UV-Vis、SEM、TEM、EDX 和 XRD 研究进行表征。制备的 Ir@PS 催化剂在使用水合肼作为还原源和环境友好的聚乙二醇 (PEG-400) 作为绿色溶剂将官能化硝基芳烃化学和区域选择性控制氢化成相应的 N-芳基羟胺方面表现出优异的反应活性。本方法应用于广泛的底物范围，并发现与广泛的可还原官能团兼容。反应在 85 °C 或环境温度下进行，并在 5–80 分钟内完成。催化剂可以很容易地从反应混合物中滤出并可重复使用。

  DOI：

  10.1016/j.mcat.2021.111836

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。
• Carbon supported Pt colloid as effective catalyst for selective hydrogenation of nitroarenes to arylhydroxylamines
  作者：Zeming Rong、Wenqiang Du、Yue Wang、Lianhai Lu

  DOI：10.1039/b916686f

  日期：——

  The Pt colloid supported on carbon is an active and selective catalyst for the partial hydrogenation of nitroaromatics with electron-withdrawing substituents to the corresponding N-arylhydroxylamine, indicating an additive-free green catalytic approach for arylhydroxylamine synthesis.

  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。
• The selective reduction of nitroarenes to N-arylhydroxylamines using Zn in a CO2/H2O system
  作者：Shijuan Liu、Yanhua Wang、Jingyang Jiang、Zilin Jin

  DOI：10.1039/b906283a

  日期：——

  Nitroarenes are reduced to the corresponding N-arylhydroxylamines with high selectivity using Zn dust in a CO2/H2O system under mild conditions. The yield of N-phenylhydroxylamine from nitrobenzene is 88% when the reaction is carried out at 25 °C for 1.5 hours with a Zn to nitrobenzene molar ratio equal to 3 under 0.1 MPa CO2. Other nitroarenes, which contain reducible functionality other than a nitro group, are also reduced to the corresponding N-arylhydroxylamines with yield from 88% to 99%. The process fully removes the need to use NH4Cl and is environmentally benign.

  在温和条件下，使用锌粉在CO2/H2O系统中能高度选择性地将硝基芳烃还原为相应的N-芳基羟胺。当反应在25°C下进行1.5小时，锌与硝基苯的摩尔比为3，CO2压力为0.1 MPa时，硝基苯转化为N-苯基羟胺的产率为88%。其他含有硝基以外可还原官能团的硝基芳烃也能以88%至99%的产率还原为相应的N-芳基羟胺。该过程完全不需要使用NH4Cl，并且对环境友好。
• 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。
• Selective reduction of nitroarenes to N-arylhydroxylamines by use of Zn in a CO2–H2O system, promoted by ultrasound
  作者：Shijuan Liu、Yanhua Wang、Xun Yang、Jingyang Jiang

  DOI：10.1007/s11164-012-0562-5

  日期：2012.11

  The promoting effect of ultrasound on the selective reduction of nitroarenes to N-arylhydroxylamines by use of Zn in an environmentally benign CO2–H2O system has been demonstrated. The yield of N-phenylhydroxylamine reaches 95 % when the reaction is carried out with a Zn-to-nitrobenzene molar ratio of 2.2 under ultrasound (40 kHz) at 25 °C and normal pressure of CO2 for 60 min. Application of ultrasound to the reaction has the advantages of higher yield of N-arylhydroxylamines, shorter reaction time, and consumption of less Zn.

  超声波在环境友好型CO2-H2O体系中通过锌选择性还原硝基芳烃至N-芳基羟胺的促进作用已被证实。在超声波（40 kHz）作用下，25°C及常压CO2条件下反应60分钟，当锌与硝基苯的摩尔比为2.2时，N-苯基羟胺的产率可达95%。将超声波应用于该反应具有N-芳基羟胺产率高、反应时间短以及锌消耗量少的优点。