2,4,6,8,10-pentaisopropylpyren-3a(3H)-ylium | 136827-92-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 2,4,6,8,10-pentaisopropylpyren-3a(3H)-ylium
• CAS: 136827-92-4
• 化学式: C₃₁H₄₁
• 分子量: 413.667
• InChiKey: JGXLSBCXQWZHQO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.63
• 重原子数：
  31.0
• 可旋转键数：
  5.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  1,3,5,7,9-pentaisopropylpyrene 在 氟磺酸 作用下， 以 liquid sulphur dioxide 为溶剂， 生成 2,4,6,8,10-pentaisopropylpyren-3a(3H)-ylium
  参考文献：
  名称：

  Protonation and sulfinylation of isomeric isopropylpyrenes, 2,7-di-tert-butylpyrene, and tetracyclohexyl- and tetracyclopentylpyrenes: remarkably stable, sterically crowded pyrenium cations

  摘要：

  1-Isopropyl- (1), 2-isopropyl- (2), 4-isopropyl- (3), 1,3,6,8-tetraisopropyl- (4), and 1,3,5,7,9-pentaisopropylpyrene (5), 2,7-di-tert-butylpyrene (6), and 1,3,5,8-tetracyclohexyl- (7) and 2,4,7,9-tetracyclopentylpyrene (8) in FSO3H or CF3SO3H (TfOH) in SO2 or SO2ClF solvent gave stable monopyrenium ions. In agreement with theory, exclusive alpha protonation occurred at low temperature (-75 --> -65-degrees-C) irrespective of the position of the substituents. The position of alpha-protonation is controlled by inductive stabilization of the alkyl (cycloalkyl) groups. Unlike hexahydropyrene which is diprotonated in FSO3H.SbF5 (1:1) Magic acid, with isopropylpyrenes stable dications could not be generated; in SO2 solvent the Wheland intermediates of sulfinylation were observed, whereas in SO2ClF solvent oxidation and monoprotonation were competitive. Charge distribution patterns in the sulfinylation sigma-complexes are similar to those of protonated pyrenium ions. Stable pyrenium cations deprotonate or desulfinylate on quenching without dealkylation or disproportionation. At higher temperatures (ca. -40-degrees-C), ipso-protonated 4 undergoes isomerization in FSO3H/SO2 solvent; other alkyl (cycloalkyl)pyrenium cations show no isomerization/disproportionation. Upon standing in Magic Acid, hexahydropyrene is oxidized to pyrene.

  DOI：

  10.1021/jo00024a018