1,3,5,8-tetracyclohexylpyrene | 78751-88-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: 1,3,5,8-tetracyclohexylpyrene
• CAS: 78751-88-9
• 化学式: C₄₀H₅₀
• 分子量: 530.837
• InChiKey: UYAJBVSSHJOEJC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.2
• 重原子数：
  40
• 可旋转键数：
  4
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,3,5,8-tetracyclohexylpyrene 在 三氟甲磺酸 作用下， 以 liquid sulphur dioxide 为溶剂， 生成
  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
• 作为产物：
  描述：

  芘 、 溴代环己烷 、 三溴化铝 生成 1,3,5,8-tetracyclohexylpyrene
  参考文献：
  名称：

  BERG A.; LAM J.; HANSEN P. E., ACTA CHEM. SCAND., 40,(1986) N 8, 665-677

  摘要：

  DOI：

文献信息

• Mono- and di-nitroalkyl-(cycloalkyl-)pyrenes in superacid media: dihydroxyiminium-(oxoiminium-)pyrenium dications; cyclisation to long-lived oxazoline-(and 1,2-oxazine-)pyrenium ions, ring opening to form nitrosoalkylpyrenium and nitroso radical cation salts with unprecedented stability
  作者：Kenneth K. Laali、Simon Bolvig、Poul Erik Hansen

  DOI：10.1039/p29950000537

  日期：——

  The low temperature protonations of sterically crowded molecules 2,4,6,8,10-pentaisopropyl-1-nitropyrene 1, 2,4,6,8,10-pentaisopropyl-1,3-dinitropyrene 12, 3,6,8,10-tetracyclohexyl-1-nitropyrene 16, 2,7-di-tert-butyl-1-nitropyrene 19, 2,7-di-tert-butyl-1,8-dinitropyrene 21, 1,3,6,8-tetraisopropyl-4-nitropyrene 23 and parent 1-nitropyrene 28, all possessing buttressed nitro groups, were studied in various superacid media under persistent ion conditions. Nitro group diprotonation was observed in all cases to give N,N-dihydroxyiminium-pyrenium (or oxoiminium-pyrenium) dications. The resulting dications derived from 1, 12, 16 and 23 undergo a facile intramolecular nitro group yclisation (which is usually complete within minutes at -75 degrees C --> room temp.) to give oxazoline-(or oxazine-)pyrenium cations 6 (and 11), 14 (and 15), 18 and 25. The charge distribution patterns (probed by C-13 and H-1 chemical shift analysis) for the iminium-pyrenium dications and their cyclised derivatives illustrate extensive charge delocalisation away from the iminium group at the alternating carbons of the periphery, similar to alkylpyrenium and fluoro(alkyl) pyrenium ions. The remote a positions carry substantial positive charge, which increases with the presence of inductively stabilising alkyl (cycloalkyl) substituents. The assignment of the iminium carbon was proved by independent synthesis and protonation of the 15-N labelled 1. Quenching of 6, 18 and 14 (containing 15) does not furnish their N-hydroxyoxazoline derivatives (like 5) nor the alkylnitropyrene precursors. Instead, the corresponding nitroso-alkylpyrenium and its derived radical cation salts (like 9a and 9RC) are obtained (EPR), which when re-dissolved in (CFSOH)-S-3-H-3 or (FSOH)-H-3 reform the cyclised pyrenium ions. Formation of persistent radical cations was also detected in some cases upon storage of the nitroalkylpyrene samples in (CFSOH)-S-3-H-3 ('TfOH') at room temperature.Ring opening of 25 and reduction upon quenching produces a different type of persistent nitrosoalkylpyrene radical (27 <-> 27a) with smaller a(N). The mechanistic aspects of nitro group cyclisation/ring opening are discussed.
• BERG A.; LAM J.; HANSEN P. E., ACTA CHEM. SCAND., 40,(1986) N 8, 665-677
  作者：BERG A.、 LAM J.、 HANSEN P. E.

  DOI：——

  日期：——
• Protonation and sulfinylation of isomeric isopropylpyrenes, 2,7-di-tert-butylpyrene, and tetracyclohexyl- and tetracyclopentylpyrenes: remarkably stable, sterically crowded pyrenium cations
  作者：Kenneth Khosrow Laali、Poul Erik Hansen

  DOI：10.1021/jo00024a018

  日期：1991.11

  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.