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Synlett 2000; 2000(2): 272-274
DOI: 10.1055/s-2000-6488
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Alkyl Methyl Carbonates as Methylating Agents. The O-Methylation of Phenols

Alvise Perosa* , Maurizio Selva, Pietro Tundo, Francesco Zordan
  • *Dipartimento di Scienze Ambientali dell'Università Ca' Foscari, Dorsoduro 2137, 30123, Venezia, Italy; Fax +39-41-2 57 86 20; E-mail: selva@unive.it/tundop@unive.it
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Publication Date:
31 December 2000 (online)

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The O-methylation reaction of a variety of phenols (ArOH: Ar = Ph, p-CH3C6H4, p-ClC6H4, o- and p-CH3COC6H4, and 2-naphthyl) can be conducted in a highly selective manner by using asymmetric alkyl methyl carbonates CH3OCOOR (R = n-Pr, 3b; n-Bu, 3d; CH3O(CH2)2O(CH2)2, 3e) as alkylating agents. For example, at 150 °C, phenol can be quantitatively converted into anisole in 4.5 h, using 2-(2-methoxyethoxy)ethyl methyl carbonate 3e in the presence of K2CO3 as a catalyst. Compared to the methylation reactions using dimethyl carbonate which require sealed pressurized reaction vessels, asymmetric alkyl methyl carbonates allow much simpler and safer alkylations at ambient pressure. The selectivity towards O-methylation is scarcely affected by the temperature (in the range of 120-150 °C), while it depends on the nature and on the amount of the solvent. DMF and triglyme (triethylene glycol dimethyl ether) have proven to be the better reaction media.

alkyl carbonates - O-alkylation - methyl selectivity - anisoles - methylation