Facile and Selective Procedure for the Synthesis of Bridged 1,2,4,5-Tetraoxanes; Strong Acids As Cosolvents and Catalysts for Addition of Hydrogen Peroxide to β-Diketones

A facile, experimentally simple, and selective method was developed for the synthesis of bridged 1,2,4,5-tetraoxanes based on the reaction of hydrogen peroxide with beta-diketones catalyzed by strong acids (H2SO4, HClO4, HBF4, or BF3). The yields of the target products vary from 44% to 77%. 1,2,4,5-Tetraoxanes can easily be separated from other reaction products by column chromatography. A high concentration of a strong acid is a key factor determining the selectivity of formation and the yield of 1,2,4,5-tetraoxanes. Unlike many compounds containing the O-O bond. which undergo rearrangements in acidic media, the resulting cyclic peroxides are quite stable under these conditions.