Acetic acid (4S,5S)-1,3,6,8-tetraisopropyl-5-nitro-4,5-dihydro-pyren-4-yl ester | 140201-44-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: Acetic acid (4S,5S)-1,3,6,8-tetraisopropyl-5-nitro-4,5-dihydro-pyren-4-yl ester
• 英文别名: [(4S,5S)-5-nitro-1,3,6,8-tetra(propan-2-yl)-4,5-dihydropyren-4-yl] acetate
• CAS: 140201-44-1
• 化学式: C₃₀H₃₇NO₄
• 分子量: 475.628
• InChiKey: IAUYKINVDBQXQO-KYJUHHDHSA-N

物化性质

• 沸点：
  579.4±50.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.2
• 重原子数：
  35
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  1,3,6,8-tetraisopropylpyrene 在 硝酸 、 溶剂黄146 作用下， 生成 4-nitro-1,3,6,8-tetraisopropylpyrene 、 Acetic acid (4S,5S)-1,3,6,8-tetraisopropyl-5-nitro-4,5-dihydro-pyren-4-yl ester
  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