Novel [1, 2, 4]-triazolo-[1, 5-a] pyrimidine derivatives were prepared by oxidative cyclization of suitable N-benzylidene-N′-pyrimidin-2-yl hydrazine precursors, followed by a Dimroth rearrangement. Reaction of 6-bromo-[1, 2, 4]-triazolo-[4, 3-a] pyrimidines with aliphatic amines under microwave irradiation gave the unexpected 5-amino compounds from an ANRORC-type mechanism. Full NMR and HRMS characterization was done for all the ...