1-(4-Nitrophenyl)-2-(2,4,6-trinitrophenyl)ethanone | 174742-24-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1-(4-Nitrophenyl)-2-(2,4,6-trinitrophenyl)ethanone
• CAS: 174742-24-6
• 化学式: C₁₄H₈N₄O₉
• 分子量: 376.239
• InChiKey: DGDLIJXZMAKEGO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  200
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  1-(4-Nitrophenyl)-2-(2,4,6-trinitrophenyl)ethanone 在 四甲基氢氧化铵 作用下， 以 水 、 二甲基亚砜 为溶剂， 生成 C₁₄H₇N₄O₉^(1-)
  参考文献：
  名称：

  Transition State Imbalances in the Deprotonation of Picrylacetophenones by Carboxylate and Phenoxide Bases

  摘要：

  The kinetics of the reversible deprotonation of 4-X-substituted picrylacetophenones 3a-c (X = NO2, H, MeO) by a variety of bases have been measured in 50% H(2)0-50%Me(2)SO (v/v) at 25 degrees C. Comparison of Bronsted PB values for the ionization of each carbon acid by phenoxide and carboxylate bases and alpha(CH) values for deprotonation of 3a-c by individual buffers bases indicates that the reaction proceeds through strongly imbalanced transition states. The intrinsic reactivities of 3a-c, as determined from the Bronsted plots for phenoxide ion reactions, are typical for the formation of resonance-stabilized polynitrobenzyl-type carbanions, but the intrinsic rate constant k(0) decreases regularly on going from the less acidic p-methoxyacetophenone derivative 3c to the more acidic p-nitroacetophenone derivative 3a. This trend is attributed to the fact that the contribution of the benzoyl moiety to the resonance stabilization of the resulting carbanion C-3 is completely negligible for the p-methoxy compound but not for the p-nitro compound. An extensive H-1 and C-13 NMR study of the ionization of 3a-c confirms this proposal, with steric hindrance to rotation of the picryl ring around the C-alpha-C-ipso linkage being observed at the probe temperature in the p-methoxy-substituted carbanion C-3c, at -40 degrees C for the unsubstituted carbanion C-3b, but not at all for the p-nitro carbanion C-3a. A major finding, however, is that the three carbanions undergo protonation at the p-nitro group of the picryl ring to form nitronic acids in acidic media. This behavior clearly shows that charge delocalization through the 2,4,6-trinitrophenyl moiety is predominant in the three systems, including C-3a.

  DOI：

  10.1021/jo9518617
• 作为产物：
  描述：

  2,4,6-三硝基甲苯 在 水 、 碳酸氢钠 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 6.0h， 生成 1-(4-Nitrophenyl)-2-(2,4,6-trinitrophenyl)ethanone
  参考文献：
  名称：

  Zbarskii; Yudin; Derevitskaya, Russian Journal of Organic Chemistry, 1997, vol. 33, # 7, p. 991 - 994

  摘要：

  DOI：

文献信息

• Zbarskii; Yudin; Derevitskaya, Russian Journal of Organic Chemistry, 1997, vol. 33, # 7, p. 991 - 994
  作者：Zbarskii、Yudin、Derevitskaya

  DOI：——

  日期：——
• Transition State Imbalances in the Deprotonation of Picrylacetophenones by Carboxylate and Phenoxide Bases
  作者：G. Moutiers、B. El Fahid、R. Goumont、A. P. Chatrousse、F. Terrier

  DOI：10.1021/jo9518617

  日期：1996.1.1

  The kinetics of the reversible deprotonation of 4-X-substituted picrylacetophenones 3a-c (X = NO2, H, MeO) by a variety of bases have been measured in 50% H(2)0-50%Me(2)SO (v/v) at 25 degrees C. Comparison of Bronsted PB values for the ionization of each carbon acid by phenoxide and carboxylate bases and alpha(CH) values for deprotonation of 3a-c by individual buffers bases indicates that the reaction proceeds through strongly imbalanced transition states. The intrinsic reactivities of 3a-c, as determined from the Bronsted plots for phenoxide ion reactions, are typical for the formation of resonance-stabilized polynitrobenzyl-type carbanions, but the intrinsic rate constant k(0) decreases regularly on going from the less acidic p-methoxyacetophenone derivative 3c to the more acidic p-nitroacetophenone derivative 3a. This trend is attributed to the fact that the contribution of the benzoyl moiety to the resonance stabilization of the resulting carbanion C-3 is completely negligible for the p-methoxy compound but not for the p-nitro compound. An extensive H-1 and C-13 NMR study of the ionization of 3a-c confirms this proposal, with steric hindrance to rotation of the picryl ring around the C-alpha-C-ipso linkage being observed at the probe temperature in the p-methoxy-substituted carbanion C-3c, at -40 degrees C for the unsubstituted carbanion C-3b, but not at all for the p-nitro carbanion C-3a. A major finding, however, is that the three carbanions undergo protonation at the p-nitro group of the picryl ring to form nitronic acids in acidic media. This behavior clearly shows that charge delocalization through the 2,4,6-trinitrophenyl moiety is predominant in the three systems, including C-3a.