TAUTOMERISM IN NEUTRAL AND DEPROTONATED 6-AMINO-5-FORMYLURACILS: A PM3-COSMO APPROACH

Abstract

In order to identify the structure of the most stable tautomers of 6-amino-5-formyluracil and its N-methylated derivatives in different pH conditions, relative stabilities of potential tautomers in aqueous phase have been calculated taking into account the entropy effects over the tautomeric equilibria. In each medium, the tautomer with lower energy must be the most representative form at the corresponding pH and the knowledge of the effect of the medium in the tautomerization energies allows evaluating the possible effect of the medium over the molecular stability. The results show that, in aqueous phase, the order of basicity of protonation sites in the 6-amino-5-formyluracil derivatives is N 9 > ( N 3 > N 1) > ( O 8 > O 4 > O 2). The 6-amino-5-formyluracil derivatives act as an amino-formyl-keto tautomer with a strong imino character, although, upon successive deprotonations, a growing contribution of enolyzed forms which explain the increasing labilization of carbonyl bonds must be pointed out.