O-Alkylation of pyrocatechol with 4-chloromethyl-1,3-dioxolane has been investigated. The ether formation selectivity is largely determined by the structure of the reactants and the conditions of the process. The inhibiting effect of the synthesized ortho-substituted phenols has been examined in the model system of radical chain oxidation of 1,4-dioxane. DOI: 10.1134/S096554411205012X