1,3,6,8-tetranitro-4-isopropylpyrene | 140175-89-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: 1,3,6,8-tetranitro-4-isopropylpyrene
• 英文别名: 1,3,6,8-Tetranitro-4-propan-2-ylpyrene
• CAS: 140175-89-9
• 化学式: C₁₉H₁₂N₄O₈
• 分子量: 424.326
• InChiKey: KWVOZSSPPZQKQS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  31
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.16
• 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：

  4-isopropylpyrene 在 nitronium tetrafluoborate 作用下， 以 乙腈 为溶剂， 以70%的产率得到1,3,6,8-tetranitro-4-isopropylpyrene
  参考文献：
  名称：

  Nitration of isopropylpyrenes. Strained models for protonation and transfer-nitration in the condensed phase

  摘要：

  Protic mono- and dinitration of 1,3,5,7,9-pentaisopropylpyrene (1) occurred at the available alpha positions to give 2 and 3. Despite steric crowding, 2 and 3 did not exhibit a torsional barrier to i-Pr rotation at ambient temperatures; however, buttressing of the peri i-Pr groups was evident (H-1 NMR, UV, and force field energy minimizations). Persistent (dihydroxyiminium)pyrenium dications 2a+2 and 3a+2 were formed by low temperature protonation of 2 and 3 with CF3SO3H (TfOH)/SO2 or with FSO3H/SO2. Intramolecular cyclization of the nitro group of 2a+2 gave the rearranged pyrenium ion 2c+. 1 reacted with NO2+BF4- in acetonitrile solvent to give two pyrenium ions stable at rt, viz. the Wheland intermediate of alpha-nitration 2b+2 and the (dihydroxyiminium)pyrenium dication 2a+2; the latter was also the predominant pyrenium ion formed in the reaction of 1 with NO+BF4- in acetonitrile. Reaction of 1 with NO2+BF4- in chloroform solvent gave alpha-nitration products and a persistent radical cation RC. The simultaneous presence of alpha-nitration products and a persistent pyrenium RC was also observed in the reaction of 1 with NO+BF4- in chloroform, where broader NMR line widths and a stronger ESR signal suggested more extensive oxidation. Protic and aprotic nitrations of 1,3,6,8-tetraisopropylpyrene (10) occurred at the alpha-beta positions; a minor addition product (26) was also found. A mixture of isomeric dinitropyrenes was obtained in NO2+ nitration of 1-isopropylpyrene (13). In line with low temperature protonation studies, aprotic nitrations of 2-isopropyl- and 4-isopropylpyrenes occurred predominantly at the alpha positions. The crowded pyrenium ion of 3 and 2 transfer nitrate to aromatics (toluene, mesitylene, benzene) under mild conditions in competition with a more facile transalkylation.

  DOI：

  10.1021/jo00035a022

文献信息

• Nitration of isopropylpyrenes. Strained models for protonation and transfer-nitration in the condensed phase
  作者：Kenneth Khosrow Laali、Tze Ming Liang、Poul Erik Hansen

  DOI：10.1021/jo00035a022

  日期：1992.4

  Protic mono- and dinitration of 1,3,5,7,9-pentaisopropylpyrene (1) occurred at the available alpha positions to give 2 and 3. Despite steric crowding, 2 and 3 did not exhibit a torsional barrier to i-Pr rotation at ambient temperatures; however, buttressing of the peri i-Pr groups was evident (H-1 NMR, UV, and force field energy minimizations). Persistent (dihydroxyiminium)pyrenium dications 2a+2 and 3a+2 were formed by low temperature protonation of 2 and 3 with CF3SO3H (TfOH)/SO2 or with FSO3H/SO2. Intramolecular cyclization of the nitro group of 2a+2 gave the rearranged pyrenium ion 2c+. 1 reacted with NO2+BF4- in acetonitrile solvent to give two pyrenium ions stable at rt, viz. the Wheland intermediate of alpha-nitration 2b+2 and the (dihydroxyiminium)pyrenium dication 2a+2; the latter was also the predominant pyrenium ion formed in the reaction of 1 with NO+BF4- in acetonitrile. Reaction of 1 with NO2+BF4- in chloroform solvent gave alpha-nitration products and a persistent radical cation RC. The simultaneous presence of alpha-nitration products and a persistent pyrenium RC was also observed in the reaction of 1 with NO+BF4- in chloroform, where broader NMR line widths and a stronger ESR signal suggested more extensive oxidation. Protic and aprotic nitrations of 1,3,6,8-tetraisopropylpyrene (10) occurred at the alpha-beta positions; a minor addition product (26) was also found. A mixture of isomeric dinitropyrenes was obtained in NO2+ nitration of 1-isopropylpyrene (13). In line with low temperature protonation studies, aprotic nitrations of 2-isopropyl- and 4-isopropylpyrenes occurred predominantly at the alpha positions. The crowded pyrenium ion of 3 and 2 transfer nitrate to aromatics (toluene, mesitylene, benzene) under mild conditions in competition with a more facile transalkylation.