Keto-enol tautomerism, NMR spectra, and H-D exchange of 4-hydroxycoumarins

Abstract

4-Hydroxycoumarin 1, 4,5-dihydroxycoumarin 2, and 4,7-dihydroxycoumarin 3 undergo H-D exchange at the C(3) atom of the lactone ring. Although only the 4-hydroxy-2-chromenone tautomeric forms are seen in the 1H and 13C NMR spectra of compounds 1-3, the equilibrium between the 4-hydroxy-2-chromenone and 2,4-chromandione forms is suggested to be the key step in the H-D exchange reaction. 4,5-Dihydroxycoumarin shows the highest rate of the reaction, since H-bonding between 5-hydroxyl and 4-keto functional groups can provide relative stability to the 5-hydroxy-2,4-chromandione tautomeric form, a probable intermediate of the exchange. NMR spectra and tautomeric transformations of 3-(4-methoxyphenylazo)-4-hydroxycoumarin 4 and 3-acetyl-4-hydroxycoumarin 5 are also discussed. The stabilities of different tautomeric forms of compounds 1-5 have been evaluated by MNDO calculations.