1,3,4,6-tetramethyl-r-3-nitro-t-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: 1,3,4,6-tetramethyl-r-3-nitro-t-6-trinitromethylcyclohexa-1,4-diene
• 英文别名: (3S,6R)-1,3,4,6-tetramethyl-3-nitro-6-(trinitromethyl)cyclohexa-1,4-diene
• 化学式: C₁₁H₁₄N₄O₈
• 分子量: 330.254
• InChiKey: GRFUPFAPABBJCA-ZJUUUORDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 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

• 作为反应物：
  描述：

  1,3,4,6-tetramethyl-r-3-nitro-t-6-trinitromethylcyclohexa-1,4-diene 以 乙腈 为溶剂， 反应 0.08h， 生成 1,2,4,5-tetramethyl-t-4-trinitromethylcyclohexa-2,5-dien-r-1-ol 、 1,2,4,5-tetramethyl-c-4-trinitromethylcyclohexa-2,5-dien-r-1-ol
  参考文献：
  名称：

  Photochemical Nitration by Tetranitromethane. Part XXXIII. Adduct Formation in the Photochemical Reactions of 1,2,4,5- and 1,2,3,5-Tetramethylbenzene.

  摘要：

  The photolysis of the charge-transfer complex of tetranitromethane and 1,2,4,5-tetramethylbenzene in dichloromethane or acetonitrile gives the epimeric 1,3,4,6-tetramethyl-3-nitro-6-trinitromethylcyclohexa-1,4-dienes 8 and 9, in addition to products of nuclear nitration 12 and side-chain modification 10, 11, and 13-18. Similar reactions of 1,2,3,5-tetramethylbenzene gave trans-1,3,5,6-tetramethyl-6-nitro-3-trinitromethylcyclohexa-1,4-diene 30 and two isomeric 'double' adducts 31 and 32, in addition to products of nuclear nitration 27 and side-chain modification 26, 28 and 29. The eliminative rearrangements of adducts 8 and 30 to give re-aromatized products in acetonitrile or [H-2(3)]acetonitrile and in [H-2]chloroform are reported. The photolysis of the charge-transfer complexes of tetranitromethane with either 1,2,4,5-tetramethylbenzene or 1,2,3,5-tetramethylbenzene in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFP) gives a marked increase in the yields of ring-nitration products 12 or 27, respectively, reactions presumed to proceed via a nitrosation-oxidation sequence. Reaction of 1,2,4,5-tetramethylbenzene with excess nitrogen dioxide in HFP also results in extensive ring nitration to give 12 and 2,3,5,6-tetramethyl-1,4-dinitrobenzene (25); the latter compound is seen as arising via the 2,3,5,6-tetramethyl- 1,4-dinitrosobenzene (34). Similar reaction of 1,2,3,5-tetramethylbenzene gives ring-nitration product 27 as the major product. X-Ray crystal structures are reported for 2,4,6-trimethyl-1-(2',2',2'-trinitroethyl)benzene (26) and trans-1,3,5,6-tetramethyl-6-nitro-3-trinitromethyl-cyclohexa-1,4-diene (30). (C) Acta Chemica Scandinavica 1996.

  DOI：

  10.3891/acta.chem.scand.50-0991
• 作为产物：
  描述：

  四硝基甲烷 、 1,2,4,5-四甲苯 以 二氯甲烷 为溶剂， 反应 4.0h， 以7.1%的产率得到1,3,4,6-tetramethyl-r-3-nitro-c-6-trinitromethylcyclohexa-1,4-diene
  参考文献：
  名称：

  Photochemical Nitration by Tetranitromethane. Part XXXIII. Adduct Formation in the Photochemical Reactions of 1,2,4,5- and 1,2,3,5-Tetramethylbenzene.

  摘要：

  The photolysis of the charge-transfer complex of tetranitromethane and 1,2,4,5-tetramethylbenzene in dichloromethane or acetonitrile gives the epimeric 1,3,4,6-tetramethyl-3-nitro-6-trinitromethylcyclohexa-1,4-dienes 8 and 9, in addition to products of nuclear nitration 12 and side-chain modification 10, 11, and 13-18. Similar reactions of 1,2,3,5-tetramethylbenzene gave trans-1,3,5,6-tetramethyl-6-nitro-3-trinitromethylcyclohexa-1,4-diene 30 and two isomeric 'double' adducts 31 and 32, in addition to products of nuclear nitration 27 and side-chain modification 26, 28 and 29. The eliminative rearrangements of adducts 8 and 30 to give re-aromatized products in acetonitrile or [H-2(3)]acetonitrile and in [H-2]chloroform are reported. The photolysis of the charge-transfer complexes of tetranitromethane with either 1,2,4,5-tetramethylbenzene or 1,2,3,5-tetramethylbenzene in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFP) gives a marked increase in the yields of ring-nitration products 12 or 27, respectively, reactions presumed to proceed via a nitrosation-oxidation sequence. Reaction of 1,2,4,5-tetramethylbenzene with excess nitrogen dioxide in HFP also results in extensive ring nitration to give 12 and 2,3,5,6-tetramethyl-1,4-dinitrobenzene (25); the latter compound is seen as arising via the 2,3,5,6-tetramethyl- 1,4-dinitrosobenzene (34). Similar reaction of 1,2,3,5-tetramethylbenzene gives ring-nitration product 27 as the major product. X-Ray crystal structures are reported for 2,4,6-trimethyl-1-(2',2',2'-trinitroethyl)benzene (26) and trans-1,3,5,6-tetramethyl-6-nitro-3-trinitromethyl-cyclohexa-1,4-diene (30). (C) Acta Chemica Scandinavica 1996.

  DOI：

  10.3891/acta.chem.scand.50-0991

文献信息

• Photochemical Nitration by Tetranitromethane. Part XXXIII. Adduct Formation in the Photochemical Reactions of 1,2,4,5- and 1,2,3,5-Tetramethylbenzene.
  作者：Craig P. Butts、Lennart Eberson、Karen L. Fulton、Michael P. Hartshorn、Ward T. Robinson、David J. Timmerman-Vaughan、Muhammed Nour Homsi、Frank K. H. Kuske、Monika Haugg、Nathalie Trabesinger-Rüf、Elmar G. Weinhold

  DOI：10.3891/acta.chem.scand.50-0991

  日期：——

  The photolysis of the charge-transfer complex of tetranitromethane and 1,2,4,5-tetramethylbenzene in dichloromethane or acetonitrile gives the epimeric 1,3,4,6-tetramethyl-3-nitro-6-trinitromethylcyclohexa-1,4-dienes 8 and 9, in addition to products of nuclear nitration 12 and side-chain modification 10, 11, and 13-18. Similar reactions of 1,2,3,5-tetramethylbenzene gave trans-1,3,5,6-tetramethyl-6-nitro-3-trinitromethylcyclohexa-1,4-diene 30 and two isomeric 'double' adducts 31 and 32, in addition to products of nuclear nitration 27 and side-chain modification 26, 28 and 29. The eliminative rearrangements of adducts 8 and 30 to give re-aromatized products in acetonitrile or [H-2(3)]acetonitrile and in [H-2]chloroform are reported. The photolysis of the charge-transfer complexes of tetranitromethane with either 1,2,4,5-tetramethylbenzene or 1,2,3,5-tetramethylbenzene in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFP) gives a marked increase in the yields of ring-nitration products 12 or 27, respectively, reactions presumed to proceed via a nitrosation-oxidation sequence. Reaction of 1,2,4,5-tetramethylbenzene with excess nitrogen dioxide in HFP also results in extensive ring nitration to give 12 and 2,3,5,6-tetramethyl-1,4-dinitrobenzene (25); the latter compound is seen as arising via the 2,3,5,6-tetramethyl- 1,4-dinitrosobenzene (34). Similar reaction of 1,2,3,5-tetramethylbenzene gives ring-nitration product 27 as the major product. X-Ray crystal structures are reported for 2,4,6-trimethyl-1-(2',2',2'-trinitroethyl)benzene (26) and trans-1,3,5,6-tetramethyl-6-nitro-3-trinitromethyl-cyclohexa-1,4-diene (30). (C) Acta Chemica Scandinavica 1996.