69804-73-5Relevant academic research and scientific papers
PREDOMINANT O-ALKYLATION IN THE ATTACK OF FREE BENZYL CATION ON 2,6-DIMETHYLANISOLE
Angelini, Giancarlo,Sparapani, Cinzia,Speranza, Maurizio
, p. 479 - 484 (2007/10/02)
Labelled benzyl cation from the decay of side-chain multitritiated toluene has been allowed to react with 2,6-dimethylanisole in n-hexane, nitromethane, and diethyl ether solutions at room temperature The nuclear-decay formed (nucleogenic) benzyl cation displays high selectivity toward the n-type centre of the nucleophiles present, leading to predominant formation of benzyl 2,6-dimethylphenyl ether in n-hexane and nitromethane, via the O-benzylated oxonium intermediate.In n-hexane, the oxonium intermediate undergoes partial isomerization, yielding the corresponding ring-substituted products (0.5 meta/para = 1.3).A mechanism involving a tight sandwich ? complex is proposed to account for the solvent effect on product distribution.The mechanistic features of the benzylation process, deduced from the decay experiments, are discussed and compared with those of related gas-phase and conventional Friedel-Crafts data.
Meta Substitution in Electrophilic Benzylations of 2,6-Dimethylphenol and Alkyl 2,6-Dimethylphenyl Ethers: Product Distributions and Mechanism
Miller, Bernard,McLaughlin, Michael P.,Marhevka, Virginia C.
, p. 710 - 719 (2007/10/02)
Electrophilic benzylations of 2,6-dimethylphenol and 2,6-dimethylanisole under a variety of conditions yield ca. 40 percent and 70percent, respectively, of the meta substitution products, although other electrophilic substitution reactions appear to proce
