Improved methodologies for synthesis of prenylated xanthones by microwave irradiation and combination of heterogeneous catalysis (K10 clay) with microwave irradiation

Abstract

Eleven prenylated xanthone derivatives ( 4– 9, 11– 15) have been synthesized for the first time by the microwave irradiation method. Prenylation of the xanthone building blocks 1 and 2 with prenyl bromide in alkaline medium, using microwave irradiation, gave the oxyprenylated xanthones 4 and 6, as major products in high yields, as well as diprenylated by-products ( 5, 7, 8, and 9) in very low yields. Microwave irradiation of oxyprenylated xanthones 4 and 6 furnished three new Claisen rearranged products ( 11, 14, and 15), as well as the previously described dihydrofuranoxanthones ( 12, 13). Furthermore, three new ( 19, 20, 21) and three previously described ( 16, 17, 18) dihydropyranoxanthones have also been prepared by a one-pot synthesis from xanthones 1, 2, and 3, using Montmorillonite K10 clay as a heterogeneous catalyst and a combination of Montmorillonite K10 clay with microwave irradiation in various conditions. The presence of solvent and the type of the clay (commercial or dry) were found to have a strong influence on the product yields. This is the first report of using these methodologies for the synthesis of dihydropyranoxanthone derivatives. The structures of the prenylated xanthones obtained were established by IR, UV, HRMS, and NMR ( 1H, 13C, HSQC, and HMBC) techniques.