1,3,5-triisopropyl-2,4,6-trinitro-benzene | 197656-63-6

• 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: 1,3,5-triisopropyl-2,4,6-trinitro-benzene
• 英文别名: 1,3,5-Triisopropyl-2,4,6-trinitro-benzol；1,3,5-Trinitro-2,4,6-tri(propan-2-yl)benzene
• CAS: 197656-63-6
• 化学式: C₁₅H₂₁N₃O₆
• 分子量: 339.348
• InChiKey: OVIYQCKETJYNKH-UHFFFAOYSA-N

物化性质

• 沸点：
  471.9±45.0 °C(Predicted)
• 密度：
  1.233±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  138
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,3,5-triisopropyl-2,4,6-trinitro-benzene 、 [1,2-bis(diphenylphosphino)ethane]tricarbonylruthenium 以 四氢呋喃 为溶剂， 生成 二氧化碳 、
  参考文献：
  名称：

  Activation of Nitroarenes in the Homogenous Catalytic Carbonylation of Nitroaromatics via an Oxygen-Atom-Transfer Mechanism Induced by Inner-Sphere Electron Transfer

  摘要：

  Kinetic and mechanistic studies on the deoxygenation of nitroarenes by Ru(dppe)(CO)(3), where dppe = 1,2-bis(diphenylphosphino)ethane, are described. The products of the reaction included 1 equiv of carbon dioxide and an eta(2)-nitrosoarene ruthenium complex (Ru(dppe)(CO)(2)[ON(Ar)] for Ar = 4-chloro-2-trifluoromethylphenyl), which was isolated and fully characterized by solution spectroscopic methods and by single crystal X-ray diffraction [monoclinic crystal system, space group P2(1)/c (#14), a = 14.556 (8) Angstrom, b = 12.903 (6) Angstrom, c = 20.10 (1) Angstrom, beta = 105.60 (6)degrees, V = 3636 (8) Angstrom(3), Z = 4]. The deoxygenation reaction was determined to be first-order with respect to both Ru(dppe)(CO)(3) and nitroarene. Electron withdrawing substituents on the nitroarene and polar solvents accelerated the rate, and a substituent study provided a rho of +3.45 indicating negative charge buildup on the nitroarene in the rate determining step of the reaction. Activation enthalpies for 2-CF3, 4-Cl, 4-H, and 4-CH3 substituted nitroarenes were 9.3, 9.9, 10.5, and 10.7 kcal mol(-1), and the entropies of activation were -35, -33, -36, and -37 eu, respectively. Correlation between the reduction potentials of the nitroarenes (E(ArNO2)degrees) and log k(2) was also observed for substituted nitroarenes yielding a slope of 10 V-1. Monosubstituted nitroarenes bearing a single methyl, phenyl, or chloro group in the ortho position and disubstituted 2,6-dimethyl- and 2,3-dichloronitrobenzene showed no attenuation in the rate, from what would be expected based on the E(ArNO2)degrees - log k(2) correlation. Large rate attenuation was observed for nitroarenes bearing both ortho and meta groups. Analysis of the kinetic and thermodynamic data using Marcus theory indicated that the rates were too high for an outer-sphere electron-transfer mechanism. The data were interpreted in terms of an inner-sphere electron-transfer mechanism where the unfavorable energetics are mitigated by bonding interactions between the donor and acceptor.

  DOI：

  10.1021/ja971899w
• 作为产物：
  描述：

  三異丙苯 在 硫酸 、 硝酸 、 乙酸酐 、 溶剂黄146 作用下， 生成 1,3,5-triisopropyl-2,4,6-trinitro-benzene
  参考文献：
  名称：

  Polyisopropylbenzenes. V. Acetylation¹

  摘要：

  DOI：

  10.1021/ja01252a062

文献信息

• Activation of Nitroarenes in the Homogenous Catalytic Carbonylation of Nitroaromatics via an Oxygen-Atom-Transfer Mechanism Induced by Inner-Sphere Electron Transfer
  作者：Steven J. Skoog、Wayne L. Gladfelter

  DOI：10.1021/ja971899w

  日期：1997.11.1

  Kinetic and mechanistic studies on the deoxygenation of nitroarenes by Ru(dppe)(CO)(3), where dppe = 1,2-bis(diphenylphosphino)ethane, are described. The products of the reaction included 1 equiv of carbon dioxide and an eta(2)-nitrosoarene ruthenium complex (Ru(dppe)(CO)(2)[ON(Ar)] for Ar = 4-chloro-2-trifluoromethylphenyl), which was isolated and fully characterized by solution spectroscopic methods and by single crystal X-ray diffraction [monoclinic crystal system, space group P2(1)/c (#14), a = 14.556 (8) Angstrom, b = 12.903 (6) Angstrom, c = 20.10 (1) Angstrom, beta = 105.60 (6)degrees, V = 3636 (8) Angstrom(3), Z = 4]. The deoxygenation reaction was determined to be first-order with respect to both Ru(dppe)(CO)(3) and nitroarene. Electron withdrawing substituents on the nitroarene and polar solvents accelerated the rate, and a substituent study provided a rho of +3.45 indicating negative charge buildup on the nitroarene in the rate determining step of the reaction. Activation enthalpies for 2-CF3, 4-Cl, 4-H, and 4-CH3 substituted nitroarenes were 9.3, 9.9, 10.5, and 10.7 kcal mol(-1), and the entropies of activation were -35, -33, -36, and -37 eu, respectively. Correlation between the reduction potentials of the nitroarenes (E(ArNO2)degrees) and log k(2) was also observed for substituted nitroarenes yielding a slope of 10 V-1. Monosubstituted nitroarenes bearing a single methyl, phenyl, or chloro group in the ortho position and disubstituted 2,6-dimethyl- and 2,3-dichloronitrobenzene showed no attenuation in the rate, from what would be expected based on the E(ArNO2)degrees - log k(2) correlation. Large rate attenuation was observed for nitroarenes bearing both ortho and meta groups. Analysis of the kinetic and thermodynamic data using Marcus theory indicated that the rates were too high for an outer-sphere electron-transfer mechanism. The data were interpreted in terms of an inner-sphere electron-transfer mechanism where the unfavorable energetics are mitigated by bonding interactions between the donor and acceptor.
• Verfahren zur Herstellung von Dinitro-polyalkylenbenzolen
  申请人：BAYER AG

  公开号：EP0575852B1

  公开（公告）日：1996-10-09
• US5367108A
  申请人：——

  公开号：US5367108A

  公开（公告）日：1994-11-22
• Polyisopropylbenzenes. V. Acetylation¹
  作者：A. Newton

  DOI：10.1021/ja01252a062

  日期：1943.12