1,2,4-三甲基-5-亚硝基苯 | 158815-55-5

• 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: 1,2,4-三甲基-5-亚硝基苯
• 英文名称: 1,2,4-trimethyl-5-nitrosobenzene
• 英文别名: 1,2,4-Trimethyl-5-nitroso-benzol；1,2,4-Trimethyl-5-nitrosobenzene
• CAS: 158815-55-5
• 化学式: C₉H₁₁NO
• 分子量: 149.192
• InChiKey: XDBFNPJWKNRALW-UHFFFAOYSA-N

物化性质

• 沸点：
  261.0±39.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  29.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,2,4-三甲基-5-亚硝基苯 、 硝酸 生成 alkaline earth salt of/the/ methylsulfuric acid
  参考文献：
  名称：

  Bamberger, Chemische Berichte, 1910, vol. 43, p. 1848

  摘要：

  DOI：
• 作为产物：
  描述：

  1,2,4-三甲基苯 在 nitrosonium tetrafluoroborate 作用下， 以 乙腈 为溶剂， 反应 5.0h， 以65%的产率得到1,2,4-三甲基-5-亚硝基苯
  参考文献：
  名称：

  Direct Nitrosation of Aromatic Hydrocarbons and Ethers with the Electrophilic Nitrosonium Cation

  摘要：

  Various polymethylbenzenes and anisoles are selectively nitrosated with the electrophilic nitrosonium salt NO+ BFI4- in good conversions and yields under mild conditions in which the conventional procedure (based on nitrite neutralization with strong acid) is ineffective. The reactivity patterns in acetonitrile deduced from the various time/conversions in Tables 2 and 3 indicate that aromatic nitrosation is distinctly different from those previously established for electrophilic aromatic nitration. The contrasting behavior of NO+ in aromatic nitrosation is ascribed to a rate-limiting deprotonation of the reversibly formed Wheland intermediate, which in the case of aromatic nitration with NO2+ occurs with no deuterium kinetic isotope effect. Aromatic nitroso derivatives (unlike the nitro counterpart) are excellent electron donors that are subject to a reversible one-electron oxidation at positive potentials significantly less than that of the parent polymethylbenzene or anisole. As a result, the series of nitrosobenzenes are also much better Bronsted bases than the corresponding nitro derivatives, and this marked distinction, therefore, accounts for the large differentiation in the deprotonation rates of their respective conjugate acids (i.e. Wheland intermediates).

  DOI：

  10.1021/jo00098a015

文献信息

• Synthesis of Nitrosobenzene Derivatives via Nitrosodesilylation Reaction
  作者：Corinna Kohlmeyer、Maike Klüppel、Gerhard Hilt

  DOI：10.1021/acs.joc.8b00262

  日期：2018.4.6

  of trimethylsilyl-substituted benzene derivatives into nitrosobenzene derivatives is reported. The optimization of the reaction conditions was performed for moderately electron-deficient, electron-rich, and sterically hindered starting materials by varying reaction time, temperature, and equivalents of NOBF4. Also, a stable intermediate of the nitrosation reaction could be characterized by 19F NMR which

  报道了三甲基甲硅烷基取代的苯衍生物的亲电子ipso-取代成亚硝基苯衍生物。通过改变反应时间，温度和NOBF 4的当量，对中度电子不足，电子富集和空间受阻的原料进行了反应条件的优化。而且，亚硝化反应的稳定中间体可以通过19 F NMR表征，该19 F NMR可以与亚硝基苯衍生物分配给NO +加成物。该配合物在水后处理中分解并释放出所需的亚硝基苯衍生物。
• Reactions between Organomercury Compounds and Nitrosyl Compounds^1,2
  作者：Lee Irvin Smith、F. Lowell Taylor

  DOI：10.1021/ja01315a043

  日期：1935.12
• Direct Nitrosation of Aromatic Hydrocarbons and Ethers with the Electrophilic Nitrosonium Cation
  作者：Eric Bosch、Jay K. Kochi

  DOI：10.1021/jo00098a015

  日期：1994.9

  Various polymethylbenzenes and anisoles are selectively nitrosated with the electrophilic nitrosonium salt NO+ BFI4- in good conversions and yields under mild conditions in which the conventional procedure (based on nitrite neutralization with strong acid) is ineffective. The reactivity patterns in acetonitrile deduced from the various time/conversions in Tables 2 and 3 indicate that aromatic nitrosation is distinctly different from those previously established for electrophilic aromatic nitration. The contrasting behavior of NO+ in aromatic nitrosation is ascribed to a rate-limiting deprotonation of the reversibly formed Wheland intermediate, which in the case of aromatic nitration with NO2+ occurs with no deuterium kinetic isotope effect. Aromatic nitroso derivatives (unlike the nitro counterpart) are excellent electron donors that are subject to a reversible one-electron oxidation at positive potentials significantly less than that of the parent polymethylbenzene or anisole. As a result, the series of nitrosobenzenes are also much better Bronsted bases than the corresponding nitro derivatives, and this marked distinction, therefore, accounts for the large differentiation in the deprotonation rates of their respective conjugate acids (i.e. Wheland intermediates).
• Bamberger, Chemische Berichte, 1910, vol. 43, p. 1848
  作者：Bamberger

  DOI：——

  日期：——