KETO-ENOL-TAUTOMERISM, NMR-SPECTRA, AND H-D EXCHANGE OF 4-HYDROXYCOUMARINS

4-Hydroxycoumarin 1, 4,5-dihydroxycoumarin 2, and 4,7-dihydroxycoumari n 3 undergo H-D exchange at the C(3) atom of the lactone ring. Althoug h only the 4-hydroxy-2-chromenone tautomeric forms are seen in the H-1 and C-13 NMR spectra of compounds 13, the equilibrium between the 4-h ydroxy-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-hydro xy-2,4-chromandione tautomeric form, a probable intermediate of the ex change. NMR spectra and tautomeric transformations of 3-(4-methoxyphen ylazo)-4-hydroxycoumarin 4 and 3-acetyl-4-hydroxycoumarin 5 are also d iscussed. The stabilities of different tautomeric forms of compounds 1 -5 have been evaluated by MNDO calculations.