Theoretical study on the intramolecular proton transfer reactions of 3-methyl-5-hydroxyisoxazole and its water complexes

The optimized structures and proton transfer reactions of 3-methyl-5-hydroxyisoxazole and its water complexes (3-M-5-HIO · (H2O)n · (n = 0-3)) were computed at B3LYP and MP2 theoretical level. The results indicates that 3-M-5-HIO has four isomers (Ecis, Etrans, K1 and K2), and the keto tautomer, and K2 is the most stable isomer in the gas phase. Hydrogen bonding between 3-M-5-HIO and the water molecules can dramatically lower the barrier by the concerted transfer mechanism. Ecis · (H2O)3 → K1 · (H2O)3 and Ecis · (H2O)2 → K2 · (H2O)2 is found to be very efficient. Comparing with the proton transfer mechanism of 5-HIO shows that the methyl substitution prevents the intramolecular proton transfer.