2,3,4-Trimethylnitrosobenzene

• 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: 2,3,4-Trimethylnitrosobenzene
• 英文别名: 1,2,3-Trimethyl-4-nitrosobenzene
• 化学式: C₉H₁₁NO
• 分子量: 149.192
• InChiKey: OQMIHXJMPSZIKC-UHFFFAOYSA-N

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

• 作为产物：
  描述：

  三甲苯 在 nitrosonium tetrafluoroborate 作用下， 以 乙腈 为溶剂， 反应 5.0h， 以67%的产率得到2,3,4-Trimethylnitrosobenzene
  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

• 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).