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 beta-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 (H(2)SO(4), HClO(4), HBF(4), or BF(3)). 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.