hydroxy-diphenyl-(pyrenyl-(1))-methane | 202974-48-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: hydroxy-diphenyl-(pyrenyl-(1))-methane
• 英文别名: Hydroxy-diphenyl-(pyrenyl-(1))-methan；Diphenyl(pyren-1-yl)methanol
• CAS: 202974-48-9
• 化学式: C₂₉H₂₀O
• 分子量: 384.477
• InChiKey: ACXSIJCBFADOCM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  30
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.03
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  hydroxy-diphenyl-(pyrenyl-(1))-methane 在 氯氟磺酰 、 氟磺酸 作用下， 生成 (1-pyrenyl)diphenylmethyl cation
  参考文献：
  名称：

  Conformational Studies of Phenyl- and (1-Pyrenyl)triarylmethylcarbenium Ions:  Semiempirical Calculations and NMR Investigations under Stable Ion Conditions

  摘要：

  Highly stable crowded carbenium ions such as (1-pyrenyl)diphenylmethylcarbenium ion (2) and 1,6-(3) and 1,8-bis(diphenylmethylenium)pyrene [dication] (4) and their dibrominated analogues (3Br and 4Br) have been studied at low and at ambient temperatures. 2 shows a conventional two-ring flip (ph,ph), whereas the disubstituted pyrene derivatives show one-ring flips (py) and two-ring flips (ph,ph) with a higher rotational barrier in agreement with AM1 calculations. A series of calculations show that the AM1 method gives the transition-state energies in best agreement with experiment. The propeller-shaped geometry of these molecules is reflected in characteristic low-frequency resonances of the phenyl rings. At low temperature, 3 and 4 exist as rotational isomers with C-2 and C-s (or C-i) symmetry. In 4, steric interaction makes the two rotamers slightly different in energy (1 kcal). For 4 or 4Br, the C-13 chemical shift differences between the C-2 and the C-s species of 4 or 4Br correlate roughly with the calculated charge differences between the C-2 and the C-s species. The charge at the C+ carbon is most extensively delocalized in 2, whereas in 3 and 4 with two C+ groups the pyrene moieties are less effective in charge delocalization.

  DOI：

  10.1021/jo9715480
• 作为产物：
  描述：

  phenylmagnesium bromide 、 alkaline earth salt of/the/ methylsulfuric acid 在 乙醚 作用下， 生成 hydroxy-diphenyl-(pyrenyl-(1))-methane
  参考文献：
  名称：

  Lund; Berg, Matematisk - Fysiske Meddelelser, 1941, vol. 18, # 9, p. 11

  摘要：

  DOI：

文献信息

• Charge Delocalization Pathways in Persistent 1-Pyrenyl-, 4-Pyrenyl-, and 2-Pyrenylmethylcarbenium Ions as Models of PAH−Epoxide Ring Opening:  NMR Studies in Superacids and AM1 Calculations
  作者：Kenneth K. Laali、Poul Erik Hansen

  DOI：10.1021/jo9707343

  日期：1997.8.1

  The relative stability, magnitude, and mode of charge delocalization into the pyrene moiety (Py) were evaluated for a series of tertiary and secondary 1-pyrenylmethylcarbenium ions PyC+R1R2 and PyC+R3H (with R-1 = R-2 = Me and Ph; R-3 = Me, Ph, CH2Ph, and (CH2)(10)Me), 4-pyrenylmethylcarbenium ions (with R-1 = R-2 = Me; R-3 = Me and Ph), and 2-pyrenylmethylcarbenium ions (with R-1 = R-2 = Me). The carbocations were generated from the corresponding carbinols by protonation with FSO3H/SO2ClF. The primary 1-pyrenyl- and 2-pyrenylmethyl cations could not be generated by ionization of their primary alcohols. Within the tertiary and the secondary carbocations, pi-charge delocalization into the pyrene moiety and the pyrenium ion character of the resulting carbocations increase in the order: 1-pyrenyl (alpha) > 4-pyrenyl (alpha beta) > 2-pyrenyl (beta). The NMR characteristics of the resulting ions are discussed and compared. The connection between charge delocalization/ stability in the regioisomeric pyrenylmethyl carbocations and the magnitude of carcinogenic activity in the benzannelated pyrenes, for which the bay-region diol-epoxides are the ultimate carcinogens, are discussed.
• Lund; Berg, Matematisk - Fysiske Meddelelser, 1941, vol. 18, # 9, p. 12
  作者：Lund、Berg

  DOI：——

  日期：——
• Lund; Berg, Matematisk - Fysiske Meddelelser, 1941, vol. 18, # 9, p. 11
  作者：Lund、Berg

  DOI：——

  日期：——
• Conformational Studies of Phenyl- and (1-Pyrenyl)triarylmethylcarbenium Ions:  Semiempirical Calculations and NMR Investigations under Stable Ion Conditions
  作者：Poul Erik Hansen、Jens Spanget-Larsen、Kenneth K. Laali

  DOI：10.1021/jo9715480

  日期：1998.3.1

  Highly stable crowded carbenium ions such as (1-pyrenyl)diphenylmethylcarbenium ion (2) and 1,6-(3) and 1,8-bis(diphenylmethylenium)pyrene [dication] (4) and their dibrominated analogues (3Br and 4Br) have been studied at low and at ambient temperatures. 2 shows a conventional two-ring flip (ph,ph), whereas the disubstituted pyrene derivatives show one-ring flips (py) and two-ring flips (ph,ph) with a higher rotational barrier in agreement with AM1 calculations. A series of calculations show that the AM1 method gives the transition-state energies in best agreement with experiment. The propeller-shaped geometry of these molecules is reflected in characteristic low-frequency resonances of the phenyl rings. At low temperature, 3 and 4 exist as rotational isomers with C-2 and C-s (or C-i) symmetry. In 4, steric interaction makes the two rotamers slightly different in energy (1 kcal). For 4 or 4Br, the C-13 chemical shift differences between the C-2 and the C-s species of 4 or 4Br correlate roughly with the calculated charge differences between the C-2 and the C-s species. The charge at the C+ carbon is most extensively delocalized in 2, whereas in 3 and 4 with two C+ groups the pyrene moieties are less effective in charge delocalization.