Alkylation and methylation reactions are important reactions in petrochemical production and form part of the reaction mechanism of many hydrocarbon transformation processes. Here, a new reaction mechanism is explored for the zeolite catalyzed methylation of arenes using quantum chemical calculations. It is proposed that the most substituted methylbenzenes, which will reside predominantly on the protonated form when adsorbed in a zeolite, can react directly with a neutral methanol molecule in the vicinity, thereby initiating the methylation reaction without having to return a proton to the zeolite surface. The calculated barriers are quite low, indicating that the suggested mechanism is plausible. This route might explain how the most substituted methylbenzenes can function as efficient reaction intermediates in the methanol to hydrocarbons reaction without themselves acting as catalyst poisons as a consequence of their high proton affinities.
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