The reactions of thiouridines and thiouracils with chloroacetaldehyde; mechanistic considerations

2-Thiouridine, 4-thiouridine and the corresponding thiouracils were quantitatively modified with aqueous chloroacetaldehyde /37 degrees C, pH 3.0--6.5/. The rate-pH dependence found for the disappearance of the substrates suggested initial S-alkylation. The unstable S-acetaldehydyl intermediates were not detected due to their further rapid transformations. The following possibilities of such transformations are discussed: 1. intramolecular addition of the endocyclic nitrogen atom to the aldehyde carbonyl group to form the "hydroxyethano" bridged compounds, 2. hydrolysis to the corresponding "oxo" analogues of the substrates, 3. hydrolysis of the N-glycoside bond. The structures of new compounds formed in these reactions were assigned on the basis of their FD-MS, UV, IR and PMR spectra. The reaction rates were similar to those found for modification of adenosine and cytidine with chloroacetaldehyde.