The reaction of 5-amino-4-cyanoformimidoylimidazoles 1a and 1b with tosyl i
socyanate proved to be a mild and efficient method for the synthesis of the
corresponding 6-amidino-2-oxopurines 5. These compounds, which were isolat
ed in almost quantitative yield, rearrange in the presence of acetic acid-D
MF to give a pyrimido[5,4-d]pyrimidin-2-one 6. The structure of compound 6
was confirmed by X-ray crystallography. The pathway for both reactions is d
iscussed. Studies on the reactivity of tosyl isocyanate with imidazoles 2,
7, 8 and 16, obtained from 1 by selective acylation of the amino or imino n
itrogen atoms, enabled clarification of the mechanism for purine formation.