o-i-propyl(trimethylsilyl)benzene | 110271-39-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: o-i-propyl(trimethylsilyl)benzene
• 英文别名: 1-(Trimethylsilyl)-2-iso-propylbenzene；trimethyl-(2-propan-2-ylphenyl)silane
• CAS: 110271-39-1
• 化学式: C₁₂H₂₀Si
• 分子量: 192.376
• InChiKey: OICZEBQNLMRZPQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.36
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  丙烷 、 三甲基苯基硅烷 在 氧气 作用下， 37.5 ℃ 、101.32 kPa 条件下， 生成 异丙苯 、 三甲基-(2-异丙基苯基)硅烷 、 m-i-propyl(trimethylsilyl)benzene 、 o-i-propyl(trimethylsilyl)benzene 、 苯
  参考文献：
  名称：

  Gas-phase alkylation of phenyltrimethylsilanes. Using the trimethylsilyl group to probe proton shifts in gaseous arenium ions

  摘要：

  The reactivity of (trimethylsilyl)benzene (TSB) and (trimethylsilyl)toluenes (TST) toward i-C3H7+ and (CH3)2F+ has been studied in the gas phase in the interval from 0.6 to 3040 Torr and from 37.5 to 100-degrees-C by mass spectrometric and radiolytic techniques. The systematic investigation of the dependence of the relative rate of the alkylation and alkyldesilylation processes promoted by i-C3H7+ on the nature and the concentration of gaseous bases has allowed an evaluation of the rate constant of the isomerization via proton 1,2-shifts of the alkylated adducts from TSB into the corresponding ions protonated ipso to the SiMe3 group. The results, i.e., k(i) = 1.6 X 10(9) s-1 at 310 K and E(i) almost-equal-to 9.5 kcal mol-1, represent the first experimental evaluation of the kinetic parameters of proton 1,2-shifts within gaseous arenium ions, generally too fast to be monitored by mass spectrometric techniques, and are in excellent agreement with theoretical and solution-chemistry studies of the model C6H7+ ion. The selectivity of the alkylation of TSB and of m- and p-TST is discussed, particularly as regards direct ipso substitution and the steric hindrance to deprotonation of the ortho-isopropylated adducts.

  DOI：

  10.1021/ja00016a003

文献信息

• Gas-phase alkylation of phenyltrimethylsilanes. Using the trimethylsilyl group to probe proton shifts in gaseous arenium ions
  作者：Marina Attina、Fulvio Cacace、Andreina Ricci

  DOI：10.1021/ja00016a003

  日期：1991.7

  The reactivity of (trimethylsilyl)benzene (TSB) and (trimethylsilyl)toluenes (TST) toward i-C3H7+ and (CH3)2F+ has been studied in the gas phase in the interval from 0.6 to 3040 Torr and from 37.5 to 100-degrees-C by mass spectrometric and radiolytic techniques. The systematic investigation of the dependence of the relative rate of the alkylation and alkyldesilylation processes promoted by i-C3H7+ on the nature and the concentration of gaseous bases has allowed an evaluation of the rate constant of the isomerization via proton 1,2-shifts of the alkylated adducts from TSB into the corresponding ions protonated ipso to the SiMe3 group. The results, i.e., k(i) = 1.6 X 10(9) s-1 at 310 K and E(i) almost-equal-to 9.5 kcal mol-1, represent the first experimental evaluation of the kinetic parameters of proton 1,2-shifts within gaseous arenium ions, generally too fast to be monitored by mass spectrometric techniques, and are in excellent agreement with theoretical and solution-chemistry studies of the model C6H7+ ion. The selectivity of the alkylation of TSB and of m- and p-TST is discussed, particularly as regards direct ipso substitution and the steric hindrance to deprotonation of the ortho-isopropylated adducts.