Syntheses based on cyclohexadienes. Part 2. Convenient synthesis of 6-alkylsalicylates, 6-alkyl-2,4-dihydroxybenzoate, and 2,5-dialkylresorcinols

Abstract

A one pot synthesis of 6-alkylsalicylates and 6-alkyl-2,4-dihydroxybenzoates is described. Cycloaddition of 1-methoxycyclohexa-1,4- or 1,3-dienes with alkylpropiolic esters results in the regiospecific formation of 2-alkyl-6- methoxybenzoates. Thus, methyl 2-methoxy-6-methyl benzoate, methyl 2,4-dimethoxy-6-methylbenzoate, methyl 2,5-dimethoxy-6-methylbenzoate, methyl 2-methoxy-4,6-dimethylbenzoate, and ethyl 2-butyl-4,6-dimethoxybenzoate, have been prepared. By making use of this method, the synthesis of two dihydroisocoumarins namely (±)-mellein (12) and (±)-6-methoxymellein (14) is described. Employing a similar strategy, a novel route to 2,5-dialkylresorcinols has been developed. Stemphol (24b) and the antibiotic DB2073 (24d) have been synthesized.