1,3,6,8-tetraisopropylpyrene | 24300-95-6

• 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-tetraisopropylpyrene
• 英文别名: 3,5,8,10-(Tetra-isopropyl)pyren；1,3,6,8-tetra(propan-2-yl)pyrene
• CAS: 24300-95-6
• 化学式: C₂₈H₃₄
• 分子量: 370.578
• InChiKey: GWSMALASBJWDQH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.5
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  1,3,6,8-tetraisopropylpyrene 在 氟磺酸 作用下， 以 liquid sulphur dioxide 为溶剂， 生成 1,3,6,8-tetraisopropyl-1,2-dihydropyren-2-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
• 作为产物：
  描述：

  1,3,6,8-tetraisopropenylpyrene 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 、 乙酸乙酯 为溶剂， 反应 3.0h， 以98%的产率得到1,3,6,8-tetraisopropylpyrene
  参考文献：
  名称：

  Isolation and X-ray structural characterization of tetraisopropylpyrene cation radical

  摘要：

  介绍了 1,3,6,8-四异丙基苯乙烯的实际合成及其单体阳离子自由基盐的分离和 X 射线结构表征。

  DOI：

  10.1039/b800168e

文献信息

• Berg, Arne; Lam, Joergen; Hansen, Poul Erik, Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry, 1986, vol. 40, # 8, p. 665 - 677
  作者：Berg, Arne、Lam, Joergen、Hansen, Poul Erik

  DOI：——

  日期：——
• 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.
• Facile one-pot fluorination of polycyclic aromatic hydrocarbons (PAHs) with N-fluoro-2,4-dinitroimidazole; scope and limitation
  作者：Kenneth K. Laali、Mutsuo Tanaka、Farhad Forohar、Michael Cheng、John C. Fetzer

  DOI：10.1016/s0022-1139(98)00224-3

  日期：1998.9

  The synthetic utility of N-fluoro-2,4-dinitro-imidazole 'NF-2,4-DNI', a recently introduced NF fluorinating agent, has been tested for direct one-pot fluorination of several classes of polycyclic aromatic hydrocarbons, PAHs, namely pyrene, crowded alkyl(cycloalkyl)-pyrenes; hexahydro- and tetrahydro-pyrene; benzo[a] anthracene; benzo[a]- and benzo[e]pyrene; perylene; 2,7-di-tert-butylphenanthrene; chrysene; 9-methylanthracene and anthracene, as well as trans-15, 16-dimethyl-dihydropyrene; azuleno[1,2-a] acenaphthylene and azulene. Although the isolated yields are modest, the ease of handling of the reagent, simple operation (reflux in dichloroethane for 3 days) and the use of 1.1 equivalent of the reagent makes the procedure quite attractive for polynuclear aromatics, avoiding multi-step operations (NO2-PAH-->NH2-PAH-->N-2(+)-PAH-->F-PAH) or the use of toxic or costly reagents (CF3OF, XeF2, etc.); it provides direct one-pot access to a variety of F-PAHs that are not readily made using other fluorinating agents. (C) 1998 Elsevier Science S.A. All rights reserved.
• Oxidation of sterically crowded alkyl(cycloalkyl)pyrenes. Persistent dications in SbF5/SO2ClF and radical cations in FSO3H/SO2
  作者：Kenneth K. Laali、Poul Erik Hansen、Edward Gelerinter、John J. Houser

  DOI：10.1021/jo00067a049

  日期：1993.7

  Sterically crowded alkylpyrenes 2-7 undergo two-electron oxidation with SbF5/SO2ClF (or SbF5.FSO3H (9:1)/SO2ClF) to give persistent alkylpyrene dications. In agreement with the charge distribution pattern observed in the parent pyrene dication and with semiempirical calculations (AM1) on isomeric monoisopropylpyrenes dications; the deshielding order C(alpha) > C(alphabeta) > C(beta) was found in their carbon-13 NMR spectra regardless of the number and position of the alkyl substituents. In most cases, the observed DELTAdelta13C for the aromatic ipso-carbon signals of the alkylpyrenium dications relative to those of 1(+2) were slightly larger than expected for a normal substituent effect in the alkylpyrene precursors. Only minor changes (DELTAdelta13C) in the unsubstituted positions were observed, except for the ring carbons in highly crowded locations for which a noticeable upfield shift was detected. The H-1 NMR spectra of alkylpyrenium dications showed a much greater substituent dependency. Low temperature reactions of the less-reactive pyrene and 2,7-di-tert-butylpyrene with SbF5/SO2ClF led primaryl to sulfonylation sigma-complexes rather than oxidation dications. Persistent alkylpyrene radical cations were found to coexist with the alkylpyrenium ions of protonation in FSO3H/SO2 (ESR detection) without any noticeable line broadening in the NMR spectra of the Wheland intermediates.
• Lund; Berg; Danske, 1946, vol. 22, # 15, p. 17,21
  作者：Lund、Berg、Danske

  DOI：——

  日期：——