Alkylation of toluene with dichloromethane in the presence of triisobutylaluminum and perfluorophenylborates

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• 作者：N. M. Bravaya ; E. E. Faingol’d ; A. N. Galiullin ; O. N. Babkina…
• 关键词：Key wordsFriedel–Crafts reaction ; toluene ; dichloromethane ; alkylation ; triisobutylaluminum ; carbenium ions ; perfluorophenylborates ; metallocene ; NMR spectroscopy
• 刊名：Russian Chemical Bulletin
• 出版年：2015
• 出版时间：September 2015
• 年：2015
• 卷：64
• 期：9
• 页码：2076-2082
• 全文大小：300 KB
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Chemistry
  Organic Chemistry
  Inorganic Chemistry
  Russian Library of Science
  
• 出版者：Springer New York
• ISSN：1573-9171
• 卷排序：64

文摘

1H NMR method showed that in systems based on triisobutylaluminum (TIBA) and triphenylcyclopropenylium [Ph₃C₃]+[B(C₆F₅)₄]–(CPB) or triphenylmethylium [Ph₃C]+[B(C₆F₅)₄]–(TB) perfluorophenylborates in a toluene–dichloromethane mixture the Friedel–Crafts process occurs with the formation of ditolylmethane (DTM) accompanied by the complete decomposition of TIBA to form isobutane. 19F NMR spectroscopy showed that the [B(C₆F₅)₄]–anion decomposes in the systems to form B(C₆F₅)₃ and HC₆F₅. The short-living [AlBu₂i]+ cation formed in the reaction of perfluorophenylborates with TIBA is assumed to be the species initiating the process. It has been shown that CPB is less reactive than TB. The addition of a stoichiometric amount of Ph₂CCpFluHfMe₂ exerts no effect on the process with the CPB-containing system but inhibits the reaction in the case of TB.