1,2,3,4-tetramethyl-r-3-nitro-c-6-trinitromethylcyclohexa-1,4-diene

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 原羧酸衍生物
• 英文名称: 1,2,3,4-tetramethyl-r-3-nitro-c-6-trinitromethylcyclohexa-1,4-diene
• 英文别名: (3S,6R)-1,2,3,4-tetramethyl-3-nitro-6-(trinitromethyl)cyclohexa-1,4-diene
• 化学式: C₁₁H₁₄N₄O₈
• 分子量: 330.254
• InChiKey: QYEOYLZUWKSECW-ZJUUUORDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  183
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  四硝基甲烷 、 四甲基萘 以 二氯甲烷 为溶剂， 反应 8.0h， 以25.1%的产率得到2,3,4,5-tetramethyl-1-trinitromethylbenzene
  参考文献：
  名称：

  Photochemical Nitration by Tetranitromethane, Part XXXI. The Photochemical Reaction of 1,2,3,4-Tetramethylbenzene and Tetranitromethane.

  摘要：

  Photolysis of the 1,2,3,4-tetramethylbenzene-tetranitromet charge-transfer complex yields the triad of 1,2,3,4-tetramethylbenzene radical cation, nitrogen dioxide and trinitromethanide ion. Recombination of this triad gives predominantly the epimeric 1,2,3,4 tetramethyl-3-nitro-6-trinitrome 1,4-dienes 8 and 9, 1,2,3,4-tetramethyl-r-5-nitro-t-6-trinitromethylcyclohexa- 1,3-diene (10) and its nitro-alkene cycloaddition product, nitro cycloadduct 11, the 'double adduct' 1,2,3,4-tetramethyl- c-2,c-5-dinitro-t-6-trinitromethylcyclohex-3-en-r-1-ol 12, 2,3,4,5-tetramethyl-1-nitrobenzene (13), and the two products of elimination or rearrangement of labile intermediate adducts, 2,3,4,5-tetramethyl-1-trinitromethylbenz (7) and 2,3,Ptrimethyl-l-nitromethylbenzene (14). Adducts 8-12, and 2,3,4,5-tetramethyl-1-trinitromethylbenzene (7) are formed by initial attack of trinitromethanide ion at a nonmethylated ring position in the radical cation of 1,2,3,4-tetramethylbenzene (6), while 2,3,4-trimethyl-1-nitromethylbenzene (14) arises from initial attack of trinitromethanide ion ipso to a 1-(4-)-methyl group in the radical cation 6(.+). Adduct formation is substantially suppressed in the photolysis of the 1,2,3,4-tetramethylbenzene-tetranitromethane charge-transfer complex in 1,1,1,3,3,3-hexafluoro-2-propanol, only the adduct elimination product 2,3,4,5-tetramethyl-1-trinitromethylbenz (7) being formed in addition to the major product, 2,3,4,5-tetramethyl-1-nitrobenzene (13). X-Ray crystal structure determinations are reported for 2,3,4,5-tetramethyl-1-trinitromethylbenz (7) and adduct 9.

  DOI：

  10.3891/acta.chem.scand.50-0735

文献信息

• Butts, Craig P.; Eberson, Lennart; Foulds, Glenn J., Acta Chemica Scandinavica, 1995, vol. 49, # 1, p. 76 - 77
  作者：Butts, Craig P.、Eberson, Lennart、Foulds, Glenn J.、Fulton, Karen L.、Hartshorn, Michael P.、Robinson, Ward T.

  DOI：——

  日期：——
• Photochemical Nitration by Tetranitromethane, Part XXXI. The Photochemical Reaction of 1,2,3,4-Tetramethylbenzene and Tetranitromethane.
  作者：Craig P. Butts、Lennart Eberson、Karen L. Fulton、Michael P. Hartshorn、Geoffrey B. Jamieson、Ward T. Robinson、Kjell Undheim、Connie N. Rosendahl、Monika Haugg、Nathalie Trabesinger-Rüf、Elmar G. Weinhold

  DOI：10.3891/acta.chem.scand.50-0735

  日期：——

  Photolysis of the 1,2,3,4-tetramethylbenzene-tetranitromet charge-transfer complex yields the triad of 1,2,3,4-tetramethylbenzene radical cation, nitrogen dioxide and trinitromethanide ion. Recombination of this triad gives predominantly the epimeric 1,2,3,4 tetramethyl-3-nitro-6-trinitrome 1,4-dienes 8 and 9, 1,2,3,4-tetramethyl-r-5-nitro-t-6-trinitromethylcyclohexa- 1,3-diene (10) and its nitro-alkene cycloaddition product, nitro cycloadduct 11, the 'double adduct' 1,2,3,4-tetramethyl- c-2,c-5-dinitro-t-6-trinitromethylcyclohex-3-en-r-1-ol 12, 2,3,4,5-tetramethyl-1-nitrobenzene (13), and the two products of elimination or rearrangement of labile intermediate adducts, 2,3,4,5-tetramethyl-1-trinitromethylbenz (7) and 2,3,Ptrimethyl-l-nitromethylbenzene (14). Adducts 8-12, and 2,3,4,5-tetramethyl-1-trinitromethylbenzene (7) are formed by initial attack of trinitromethanide ion at a nonmethylated ring position in the radical cation of 1,2,3,4-tetramethylbenzene (6), while 2,3,4-trimethyl-1-nitromethylbenzene (14) arises from initial attack of trinitromethanide ion ipso to a 1-(4-)-methyl group in the radical cation 6(.+). Adduct formation is substantially suppressed in the photolysis of the 1,2,3,4-tetramethylbenzene-tetranitromethane charge-transfer complex in 1,1,1,3,3,3-hexafluoro-2-propanol, only the adduct elimination product 2,3,4,5-tetramethyl-1-trinitromethylbenz (7) being formed in addition to the major product, 2,3,4,5-tetramethyl-1-nitrobenzene (13). X-Ray crystal structure determinations are reported for 2,3,4,5-tetramethyl-1-trinitromethylbenz (7) and adduct 9.