Abstract The condensation of malonoaldehyde derivatives with either a 3-amino-[1, 2, 4]- triazole or a 3, 5-diamino-[1, 2, 4]-triazole precursor was studied. In agreement with previous reports, two different bicycles, namely, bearing the regioisomeric [1, 2, 4] triazolo [1, 5-a] pyrimidine (1) or [1, 2, 4] triazolo [4, 3-a] pyrimidine (2) structural surrogates, could be obtained. We found that, depending on the triazole precursor, only one regioisomer ...