1-methoxy-4-methyl-t-6-nitro-r-3-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-methoxy-4-methyl-t-6-nitro-r-3-trinitromethylcyclohexa-1,4-diene
• 英文别名: (3R,6S)-1-methoxy-4-methyl-6-nitro-3-(trinitromethyl)cyclohexa-1,4-diene
• 化学式: C₉H₁₀N₄O₉
• 分子量: 318.2
• InChiKey: GKBZSWSEOQXVTH-RQJHMYQMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  22
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  193
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  对甲苯甲醚 、 四硝基甲烷 以 二氯甲烷 为溶剂， 反应 1.0h， 以47%的产率得到4-甲氧基-3-(三硝基甲基)甲苯
  参考文献：
  名称：

  Photochemical Nitration by Tetranitromethane. Part XXVII. Adduct Formation in the Photochemical Reaction of 4-Methylanisole. Solvent and Temperature Effects on the Regiochemistry of Reaction of the Radical Cation of 4-Methylanisole.

  摘要：

  The photolysis of the charge-transfer complex of 4-methylanisole and tetranitromethane in dichloromethane gives four isomeric nitro-trinitromethyl adducts, including the epimeric 1-methoxy-4-methyl-3-nitro-6-trinitromethylcyclohexa-1,4- dienes 3 and 4 and the epimeric 1-methoxy-3-methyl-6-nitro-3-trinitromethyl-cyclohexa-1,4-dienes 5 and 6, 4-methyl-2-trinitromethylanisole 1,4-methyl-2-nitroanisole 2, nitrophenols 7 and 9, and 4-methyl-4-nitrocyclohexa-2,5-dienone 8. Similar reaction in acetonitrile also gives these products, with the exception of two of the adducts (3 and 4). The effect of reaction temperature on the yields of the various products indicates that they are formed either by attack of trinitromethanide ion on the radical cation of 4-methylanisole vicinal to the methoxy group at C2 (1, 3 and 4), or by attack of trinitromethanide ipso to the methoxy group (2, 5, 6 and 8). By conducting the photolysis in dichloromethane with trifluoroacetic acid present, the trinitromethanide pathway is eliminated, and the products formed are derived from reaction between 4-methylanisole and/or its radical cation and NO2.The effects of added Baits Bu(4)N(+)ClO(4)(-) (TBAP) or Bu(4)N(+)C(NO2)(3)(-) (TBAT) to reactions in dichloromethane are seen as the consequences of changes in the polarity of the solvent and nor to competition between ion-pair and radical-pair collapse during the reactions. By analogy with adducts 3 and 4, two adducts 16 and 17 derived from similar photolysis reactions of 4-chloroanisole are shown to be the epimeric 4-chloro-1-methoxy-3-nitro-6-trinitromethylcyclohexa-1,4-dienes 16 and 17 rather than nitrito(or hydroxy)-trinitromethyl adducts. The X-ray crystal structure of 1-methoxy-4-methyl-r-3-nitro-c-6-trinitr diene 3 is reported.

  DOI：

  10.3891/acta.chem.scand.50-0122

文献信息

• Photochemical Nitration by Tetranitromethane. Part XXVII. Adduct Formation in the Photochemical Reaction of 4-Methylanisole. Solvent and Temperature Effects on the Regiochemistry of Reaction of the Radical Cation of 4-Methylanisole.
  作者：Craig P. Butts、Lennart Eberson、Michael P. Hartshorn、Ward T. Robinson、Markku Leskelä、Mika Polamo、Muhammed Nour Homsi、Frank K. H. Kuske、Monika Haugg、Nathalie Trabesinger-Rüf、Elmar G. Weinhold

  DOI：10.3891/acta.chem.scand.50-0122

  日期：——

  The photolysis of the charge-transfer complex of 4-methylanisole and tetranitromethane in dichloromethane gives four isomeric nitro-trinitromethyl adducts, including the epimeric 1-methoxy-4-methyl-3-nitro-6-trinitromethylcyclohexa-1,4- dienes 3 and 4 and the epimeric 1-methoxy-3-methyl-6-nitro-3-trinitromethyl-cyclohexa-1,4-dienes 5 and 6, 4-methyl-2-trinitromethylanisole 1,4-methyl-2-nitroanisole 2, nitrophenols 7 and 9, and 4-methyl-4-nitrocyclohexa-2,5-dienone 8. Similar reaction in acetonitrile also gives these products, with the exception of two of the adducts (3 and 4). The effect of reaction temperature on the yields of the various products indicates that they are formed either by attack of trinitromethanide ion on the radical cation of 4-methylanisole vicinal to the methoxy group at C2 (1, 3 and 4), or by attack of trinitromethanide ipso to the methoxy group (2, 5, 6 and 8). By conducting the photolysis in dichloromethane with trifluoroacetic acid present, the trinitromethanide pathway is eliminated, and the products formed are derived from reaction between 4-methylanisole and/or its radical cation and NO2.The effects of added Baits Bu(4)N(+)ClO(4)(-) (TBAP) or Bu(4)N(+)C(NO2)(3)(-) (TBAT) to reactions in dichloromethane are seen as the consequences of changes in the polarity of the solvent and nor to competition between ion-pair and radical-pair collapse during the reactions. By analogy with adducts 3 and 4, two adducts 16 and 17 derived from similar photolysis reactions of 4-chloroanisole are shown to be the epimeric 4-chloro-1-methoxy-3-nitro-6-trinitromethylcyclohexa-1,4-dienes 16 and 17 rather than nitrito(or hydroxy)-trinitromethyl adducts. The X-ray crystal structure of 1-methoxy-4-methyl-r-3-nitro-c-6-trinitr diene 3 is reported.