(2,3,4,5-Tetramethylphenyl)methyl nitrite | 156146-36-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2,3,4,5-Tetramethylphenyl)methyl nitrite
• CAS: 156146-36-0
• 化学式: C₁₁H₁₅NO₂
• 分子量: 193.246
• InChiKey: JIUFXCXIYMDSBY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  四硝基甲烷 、 五甲基苯 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 (2,3,4,5-Tetramethylphenyl)nitromethane 、 2,3,4,5-Tetramethylbenzylnitrat 、 2,3,4,6-tetramethylbenzyl nitrate 、 1,2,3,4,5-五甲基-6-[(2,3,4,5-四甲基苯基)甲基]苯 、 (2,3,4,5-Tetramethylphenyl)methyl nitrite 、 (3R,6R)-1,2,3,4,6-pentamethyl-3-nitro-6-(trinitromethyl)cyclohexa-1,4-diene
  参考文献：
  名称：

  Photochemical Nitration by Tetranitromethane. Part XXXIV. The Photochemical Reactions of Pentamethylbenzene and Hexamethylbenzene with Tetranitromethane. The Formation and Rearrangement of Labile Adducts from Pentamethylbenzene.

  摘要：

  The photolysis of the charge transfer (CT) complex of tetranitromethane and pentamethylbenzene (13) in dichloromethane at -50 or -78 degrees C gives the labile epimeric 1,2,3,4,6-pentamethyl-3-nitro-6-trinitromethylcyclohexa-1,4-dienes 18 and 19. Adduct 18 rearranges rapidly in [H-2(2)]dichloromethane at 22 degrees C (half-life 9 min) to give 2,3,4,5-tetramethyl-1-(2',2',2'-trinitroethyl)benzene (21), 2,3,4,5-tetramethylphenylnitromethane (26), 2,3,4,5-tetramethylbenzyl nitrate (32) and 2,3,4,5-tetramethylbenzyl nitrite (36). The photolysis of the tetranitromethane-13 CT complex in dichloromethane at 20 degrees C gives compounds 21, 26, 32 and 36, in addition to their 2,3,4,6-tetramethyl analogues 20, 25, 31 and 35, the latter set of products probably arising from the rearrangement of the highly labile epimeric 1,2,3,5,6-pentamethyl-3-nitro-6-trinitromethylcyclohexa-1,4-dienes 54. The photolysis of the tetranitromethane-13 CT complex in acetonitrile gives mainly the phenylnitromethane 26, while similar reaction in 1,1,1,3,3,3-hexafluoropropan-2-ol yields pentamethylnitrobenzene 24, the latter by a nitrosation/oxidation sequence. Reaction of 13 with nitrogen dioxide in dichloromethane gives mainly compounds 26 and 30.No adducts were detected in the photolysis of the CT complex of hexamethylbenzene 14 in dichloromethane at accessible reaction temperatures (greater than or equal to-20 degrees C), but products of side-chain modification 37-46 were formed. In acetonitrile similar reaction gave in addition to the above products 37-46 the N-nitrosoacetamide 47 and its precursor 49. Compounds 47 and 49 are also formed, along with the major products pentamethylbenzyl nitrate 39 and the mono- and di-nitromethyl compounds 40 and 43, on reaction of 14 with nitrogen dioxide in acetonitrile.EPR spectroscopic examination of the photolysis of acidic (trifluoroacetic ) solutions of tetranitromethane and 13 or 14 demonstrated the formation of the corresponding radical cation or a transformation product thereof, i.e. the 1,2,3,4,5,6,7,8-octamethylanthracene radical cation from 13 or 14(.+) from 14.

  DOI：

  10.3891/acta.chem.scand.50-1121

文献信息

• Photochemical Nitration by Tetranitromethane. Part XXXIV. The Photochemical Reactions of Pentamethylbenzene and Hexamethylbenzene with Tetranitromethane. The Formation and Rearrangement of Labile Adducts from Pentamethylbenzene.
  作者：Lennart Eberson、Michael P. Hartshorn、David J. Timmerman-Vaughan、Yincai Su、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.50-1121

  日期：——

  The photolysis of the charge transfer (CT) complex of tetranitromethane and pentamethylbenzene (13) in dichloromethane at -50 or -78 degrees C gives the labile epimeric 1,2,3,4,6-pentamethyl-3-nitro-6-trinitromethylcyclohexa-1,4-dienes 18 and 19. Adduct 18 rearranges rapidly in [H-2(2)]dichloromethane at 22 degrees C (half-life 9 min) to give 2,3,4,5-tetramethyl-1-(2',2',2'-trinitroethyl)benzene (21), 2,3,4,5-tetramethylphenylnitromethane (26), 2,3,4,5-tetramethylbenzyl nitrate (32) and 2,3,4,5-tetramethylbenzyl nitrite (36). The photolysis of the tetranitromethane-13 CT complex in dichloromethane at 20 degrees C gives compounds 21, 26, 32 and 36, in addition to their 2,3,4,6-tetramethyl analogues 20, 25, 31 and 35, the latter set of products probably arising from the rearrangement of the highly labile epimeric 1,2,3,5,6-pentamethyl-3-nitro-6-trinitromethylcyclohexa-1,4-dienes 54. The photolysis of the tetranitromethane-13 CT complex in acetonitrile gives mainly the phenylnitromethane 26, while similar reaction in 1,1,1,3,3,3-hexafluoropropan-2-ol yields pentamethylnitrobenzene 24, the latter by a nitrosation/oxidation sequence. Reaction of 13 with nitrogen dioxide in dichloromethane gives mainly compounds 26 and 30.No adducts were detected in the photolysis of the CT complex of hexamethylbenzene 14 in dichloromethane at accessible reaction temperatures (greater than or equal to-20 degrees C), but products of side-chain modification 37-46 were formed. In acetonitrile similar reaction gave in addition to the above products 37-46 the N-nitrosoacetamide 47 and its precursor 49. Compounds 47 and 49 are also formed, along with the major products pentamethylbenzyl nitrate 39 and the mono- and di-nitromethyl compounds 40 and 43, on reaction of 14 with nitrogen dioxide in acetonitrile.EPR spectroscopic examination of the photolysis of acidic (trifluoroacetic ) solutions of tetranitromethane and 13 or 14 demonstrated the formation of the corresponding radical cation or a transformation product thereof, i.e. the 1,2,3,4,5,6,7,8-octamethylanthracene radical cation from 13 or 14(.+) from 14.