2-(2',4',6'-trimethylphenyl)-1-nitro-2-trinitromethylethane | 209798-32-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2-(2',4',6'-trimethylphenyl)-1-nitro-2-trinitromethylethane
• 英文别名: 1,3,5-Trimethyl-2-(1,1,1,3-tetranitropropan-2-yl)benzene
• CAS: 209798-32-3
• 化学式: C₁₂H₁₄N₄O₈
• 分子量: 342.265
• InChiKey: DVBJKLMMKKUTTO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  183
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-(2',4',6'-trimethylphenyl)-1-nitro-2-trinitromethylethane 在 2,6-二甲基吡啶 作用下， 以 氘代氯仿 为溶剂， 反应 0.3h， 生成 (E)-1,3,5-trimethyl-2-(2-nitrovinyl)benzene
  参考文献：
  名称：

  Photochemical Nitration by Tetranitromethane. Part XLIV. Some Reactions of 2-Phenylpropene and 2,4,6-Trimethylstyrene with Tetranitromethane: Competition between the Radical Chain Addition Reaction and Isoxazolidine Formation: Nitrogen Inversion in Some Isoxazolidines.

  摘要：

  Reaction of 2-phenylpropene with tetranitromethane in dichloromethane occurs either slowly in the dark or more rapidly photochemically to give 1-nitro-2-phenyl-2-trinitromethylpropane (1) and the two diastereomers of 5-methyl-2-(2'-nitro-1'-phenyl)ethoxy-3,3-dinitro-5-phenylisoxazolidine (5 and 6). In diethyl ether solution these products are also formed, but the yields of 5 and 6 are increased at the expense of the nitro-trinitromethyl adduct 1. At 23 degrees C in [H-2]chloroform solution each isoxazolidine 5 and 6 exists as two N-invertimers. Variable temperature H-1 NMR studies of 5 and 6 revealed band broadening and coalescence of all signals in the temperature range 50-100 degrees C; the rate constants and corresponding free energies of activation were identical for the two isoxazolidines 5 and 6, Delta G double dagger=74.7(5) kJ mol(-1) at 353 K. A single-crystal X-ray analysis of isoxazolidine 5 is reported.Photolysis of 2,4,6-trimethylstyrene with tetranitromethane in either dichloromethane or acetonitrile gives the nitro-trinitromethyl adduct, 2-(2',4',6'-trimethylphenyl)-1-nitro-2-trinitromethylethane (9), and nitromethyl 2,4,6-trimethylphenyl ketone (10).Base-catalysed eliminations of nitroform from adducts 1 and 9 give the corresponding (E)-nitro alkenes 7 and 11, respectively, kinetic studies showing that the rate of elimination from the secondary but sterically more compressed trinitromethyl compound 9 was greater (x15) than for the tertiary trinitromethyl compound 1.The modes of formation of adducts 1 and 9, isoxazolidines 5 and 6, and nitro ketone 10 are discussed.

  DOI：

  10.3891/acta.chem.scand.52-0761
• 作为产物：
  描述：

  四硝基甲烷 、 2,4,6-三甲基苯乙烯 以 二氯甲烷 为溶剂， 反应 0.75h， 以58.0%的产率得到2-(2',4',6'-trimethylphenyl)-1-nitro-2-trinitromethylethane
  参考文献：
  名称：

  Photochemical Nitration by Tetranitromethane. Part XLIV. Some Reactions of 2-Phenylpropene and 2,4,6-Trimethylstyrene with Tetranitromethane: Competition between the Radical Chain Addition Reaction and Isoxazolidine Formation: Nitrogen Inversion in Some Isoxazolidines.

  摘要：

  Reaction of 2-phenylpropene with tetranitromethane in dichloromethane occurs either slowly in the dark or more rapidly photochemically to give 1-nitro-2-phenyl-2-trinitromethylpropane (1) and the two diastereomers of 5-methyl-2-(2'-nitro-1'-phenyl)ethoxy-3,3-dinitro-5-phenylisoxazolidine (5 and 6). In diethyl ether solution these products are also formed, but the yields of 5 and 6 are increased at the expense of the nitro-trinitromethyl adduct 1. At 23 degrees C in [H-2]chloroform solution each isoxazolidine 5 and 6 exists as two N-invertimers. Variable temperature H-1 NMR studies of 5 and 6 revealed band broadening and coalescence of all signals in the temperature range 50-100 degrees C; the rate constants and corresponding free energies of activation were identical for the two isoxazolidines 5 and 6, Delta G double dagger=74.7(5) kJ mol(-1) at 353 K. A single-crystal X-ray analysis of isoxazolidine 5 is reported.Photolysis of 2,4,6-trimethylstyrene with tetranitromethane in either dichloromethane or acetonitrile gives the nitro-trinitromethyl adduct, 2-(2',4',6'-trimethylphenyl)-1-nitro-2-trinitromethylethane (9), and nitromethyl 2,4,6-trimethylphenyl ketone (10).Base-catalysed eliminations of nitroform from adducts 1 and 9 give the corresponding (E)-nitro alkenes 7 and 11, respectively, kinetic studies showing that the rate of elimination from the secondary but sterically more compressed trinitromethyl compound 9 was greater (x15) than for the tertiary trinitromethyl compound 1.The modes of formation of adducts 1 and 9, isoxazolidines 5 and 6, and nitro ketone 10 are discussed.

  DOI：

  10.3891/acta.chem.scand.52-0761