1,5,6-trimethyl-t-6-nitro-r-3-trinitromethylcyclohexa-1,4-diene | 175287-22-6

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: 1,5,6-trimethyl-t-6-nitro-r-3-trinitromethylcyclohexa-1,4-diene
• CAS: 175287-22-6
• 化学式: C₁₀H₁₂N₄O₈
• 分子量: 316.227
• InChiKey: NLWUXIQOEOKVMZ-KYZUINATSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.03
• 重原子数：
  22.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  172.56
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  1,5,6-trimethyl-t-6-nitro-r-3-trinitromethylcyclohexa-1,4-diene 在 2,6-二叔丁基-4-甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 3,4,5-trimethyl-1-trinitromethylbenzene
  参考文献：
  名称：

  Photochemical Nitration by Tetranitromethane. Part XXVI. Adduct Formation in the Photochemical Reaction of 1,2,3-Trimethylbenzene: the Formation of 'Double' Adducts Including Nitronic Esters.

  摘要：

  The photolysis of the charge-transfer complex of 1,2,3-trimethylbenzene and tetranitromethane gives a complex mixture of products, most of which arise by initial attack of trinitromethanide ion on the unsubstituted ring positions at C4(C6) and C5 of the radical cation of 1,2,3-trimethylbenzene. The products 7-19 are adducts resulting directly or indirectly from the addition of the elements of tetranitromethane to 1,2,3-trimethylbenzene, and the trinitromethyl aromatic compounds 22-25 are formed by eliminations from intermediate adducts. Six adducts are simple 'single' adducts, nitro-trinitromethyl adducts 7, 8, 10-12, while nitro cycloadduct 9 is formed by cycloaddition of nitro-trinitromethyl adduct 8. The remaining addition products are 'double' adducts, formed by secondary addition reactions initiated by attack of nitrogen dioxide on the buta-1,3-diene system of 'single' adducts, and include trinitro-trinitromethyl compounds 13 and 15, the hydroxy-dinitro-trinitromethyl compound 14, and a group of four nitronic esters 16-19 formed by nitro-denitrocyclization of initially formed hydroxy-trinitromethyl and nitro-trinitromethyl 'single' adducts. Minor amounts of other products are formed including two nitrodienones 21 and 22, and the rearrangement product, 4,5,6-trimethyl-2-nitrophenol (28), and the 2,3,4-trimethyl- and 3,4,5-trimethylnitrobenzenes 26 and 27.The modes of formation of the above products are discussed, and X-ray crystal structure determinations are reported for compounds 9, 13, 14, 18, 19, 22 and 29.

  DOI：

  10.3891/acta.chem.scand.50-0029
• 作为产物：
  描述：

  四硝基甲烷 、 三甲苯 以 二氯甲烷 为溶剂， 反应 4.0h， 以10.0%的产率得到1,5,6-trimethyl-c-6-nitro-r-3-trinitromethylcyclohexa-1,4-diene
  参考文献：
  名称：

  Photochemical Nitration by Tetranitromethane. Part XXVI. Adduct Formation in the Photochemical Reaction of 1,2,3-Trimethylbenzene: the Formation of 'Double' Adducts Including Nitronic Esters.

  摘要：

  The photolysis of the charge-transfer complex of 1,2,3-trimethylbenzene and tetranitromethane gives a complex mixture of products, most of which arise by initial attack of trinitromethanide ion on the unsubstituted ring positions at C4(C6) and C5 of the radical cation of 1,2,3-trimethylbenzene. The products 7-19 are adducts resulting directly or indirectly from the addition of the elements of tetranitromethane to 1,2,3-trimethylbenzene, and the trinitromethyl aromatic compounds 22-25 are formed by eliminations from intermediate adducts. Six adducts are simple 'single' adducts, nitro-trinitromethyl adducts 7, 8, 10-12, while nitro cycloadduct 9 is formed by cycloaddition of nitro-trinitromethyl adduct 8. The remaining addition products are 'double' adducts, formed by secondary addition reactions initiated by attack of nitrogen dioxide on the buta-1,3-diene system of 'single' adducts, and include trinitro-trinitromethyl compounds 13 and 15, the hydroxy-dinitro-trinitromethyl compound 14, and a group of four nitronic esters 16-19 formed by nitro-denitrocyclization of initially formed hydroxy-trinitromethyl and nitro-trinitromethyl 'single' adducts. Minor amounts of other products are formed including two nitrodienones 21 and 22, and the rearrangement product, 4,5,6-trimethyl-2-nitrophenol (28), and the 2,3,4-trimethyl- and 3,4,5-trimethylnitrobenzenes 26 and 27.The modes of formation of the above products are discussed, and X-ray crystal structure determinations are reported for compounds 9, 13, 14, 18, 19, 22 and 29.

  DOI：

  10.3891/acta.chem.scand.50-0029