1-(4-tert-butylphenyl)-2-phenylethane

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1-(4-tert-butylphenyl)-2-phenylethane
• 英文别名: 1-(4-tert-butylphenyl)-2-[D5]phenylethane
• 化学式: C₁₈H₂₂
• 分子量: 243.333
• InChiKey: KFPRNBJQLRAVCX-UPKDRLQUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.77
• 重原子数：
  18.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  benzyltriphenylphosphonium bromide 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 生成 1-(4-tert-butylphenyl)-2-phenylethane
  参考文献：
  名称：

  Intermediate ion-neutral complexes formed during the gas-phase protonolysis ofp-(tert-butyl)-substituted α,ω-diphenylalkanes

  摘要：

  AbstractLoss of isobutane is the exclusive fragmentation channel of long‐lived protonated tert‐butyl‐substituted α,ω‐diphenylalkanes with chain lengths n = 2–12. Methane chemical ionization/mass‐analysed ion kinetic energy spectrometry of the [M + H]+ ions and several deuterium‐labelled tert‐butyl‐substituted 1,2‐, 1,3‐ and 1,10‐diphenylalkanes revealed that the reaction involves with equal probability and maximum regioselectivity a hydride ion from both the adjacent and the remote benzylic methylene groups, irrespective of the length of the aliphatic chain. The isotope effect of the hydride abstraction step was found to be same in all cases, k[C4H10]/k[C4H9D] = 1.6 ± 0.1. A sterically restricted system, protonated 1‐benzyl‐4‐(tert‐butylbenzyl)benzene, shows the same behaviour. This implies, as a general phenomenon, the formation of intermediate ion–neutral complexes [C4H9+ Ar(CH2)n Ar] along with (or instead of) the corresponding π complexes [C4H9+ …︁ Ar(CH2)nAr] prior to isobutane elimination (Ar represents a phenyl or substituted‐phenyl group).

  DOI：

  10.1002/oms.1210281016

文献信息

• Interannular proton transfer in thermal arenium ions from the gas-phase alkylation of 1,2-diphenylethane
  作者：Fulvio Cacace、Maria Elisa Crestoni、Simonetta Fornarini、Dietmar Kuck

  DOI：10.1021/ja00056a029

  日期：1993.2

  function of the arenium ions' lifetime, the rate constant for the H+(D+) ring-to-ring transfer in the para-substituted arenium ions has been estimated to be (1.3 +/- 0.4) x 10(7) ((2.9 +/- 0.6) x 10(6)) s-1 at 47-degrees-C. A temperature-dependence study covering the range from 47 to 150-degrees-C has allowed the evaluation of the Arrhenius parameters for the interannular H+(D+) transfer, giving E(a) = 6

  气态双环铼离子中的热环间质子转移的首次演示及其阿伦尼乌斯参数的评估已通过辐射分解技术实现。模型离子是通过 C6D5CH2CH2C6H5 在异丁烷中在足够高的压力 (630-1730 Torr) 下用辐射分解形成的 Me3C+ 离子烷基化获得的，以确保感兴趣的过程服从热动力学。从烷基化产物中环间 H/D 加扰的“帐篷”来看，作为铷离子寿命的函数进行测量，对位取代的铕离子中 H+(D+) 环到环转移的速率常数具有在 47 摄氏度时估计为 (1.3 +/- 0.4) x 10(7) ((2.9 +/- 0.6) x 10(6)) s-1。一项涵盖 47 至 150 摄氏度范围的温度依赖性研究允许评估环间 H+(D+) 转移的阿伦尼乌斯参数，给出 E(a) = 6.3 +/- 0.2 (8.0 +/- 0.2 ) kcal mol-l 和 log A = 11.4 +/- 0.4 (11.9 +/-
• Internal Solvation Effects on the Reactivity of .alpha.,.omega.-Diphenylalkanes toward Me3C+ Ions
  作者：Maria Elisa Crestoni、Simonetta Fornarini、Dietmar Kuck

  DOI：10.1021/j100010a026

  日期：1995.3

  The reactivity of alpha,omega-diphenylalkanes (1 less than or equal to n less than or equal to 4) toward Me(3)C(+) ions has been investigated with the radiolytic technique at 720 Torr, at temperatures of 47 and 120 degrees C. The intramolecular isotopic discrimination of Me(3)C(+), favoring attack at the unlabeled ring of C6H5(CH2)(2)C6D5 by a factor of 1.5 at 120 degrees C, contrasts with the lack of intermolecular isotopic discrimination, reflected by the same reactivity toward (C6H5CH2)(2) and (C6D5CH2)(2). Competition experiments show an appreciably higher reactivity of Ph(CH2)(n)Ph (n = 2-4) relative to toluene and diphenylmethane (DPM), but, when Ph(CH2)(n)Ph (n = 3, 4) or (3-CH3C6H4)(CH2)(2)C6H5 compete with Ph(CH2)(2)Ph, relative reactivities level off. The lack of substrate selectivity, in contrast to an intramolecular discrimination in the tert-butylation of (3-CH3C6H4)(CH2)(2)C6H5 of a factor of 2, together with the related variation of kinetic isotope effects, points out the kinetic role of the collision complex 1 from Me(3)C(+) and diphenylalkanes. The additional (''spectator'') ring of the higher homologues Ph(CH2)(n)Ph (n = 2-4) prevents dissociation of 1, making its formation irreversible and causing tert-butylation to occur at the encounter rate, in contrast to DPM, whose second ring appears essentially inert. Experiments involving substitution by Me(3)Si(+) at 120 degrees C show that this electrophile attacks preferably the unlabeled ring of C6H5(CH2)(2)C6D5 by a factor of 1.5, consistent with the 1.4 times higher reactivity toward (C6H5CH2)(2) With respect to (C6D5CH2)(2). In this case, the isotopic discrimination is traced to the competition between desilylation and deprotonation of intermediate ipso-silylated arenium ions.
• Intermediate ion-neutral complexes formed during the gas-phase protonolysis ofp-(tert-butyl)-substituted α,ω-diphenylalkanes
  作者：Carsten Matthias、Dietmar Kuck

  DOI：10.1002/oms.1210281016

  日期：1993.10

  AbstractLoss of isobutane is the exclusive fragmentation channel of long‐lived protonated tert‐butyl‐substituted α,ω‐diphenylalkanes with chain lengths n = 2–12. Methane chemical ionization/mass‐analysed ion kinetic energy spectrometry of the [M + H]+ ions and several deuterium‐labelled tert‐butyl‐substituted 1,2‐, 1,3‐ and 1,10‐diphenylalkanes revealed that the reaction involves with equal probability and maximum regioselectivity a hydride ion from both the adjacent and the remote benzylic methylene groups, irrespective of the length of the aliphatic chain. The isotope effect of the hydride abstraction step was found to be same in all cases, k[C4H10]/k[C4H9D] = 1.6 ± 0.1. A sterically restricted system, protonated 1‐benzyl‐4‐(tert‐butylbenzyl)benzene, shows the same behaviour. This implies, as a general phenomenon, the formation of intermediate ion–neutral complexes [C4H9+ Ar(CH2)n Ar] along with (or instead of) the corresponding π complexes [C4H9+ …︁ Ar(CH2)nAr] prior to isobutane elimination (Ar represents a phenyl or substituted‐phenyl group).