Synthesis of (pyridinyl)-1,2,4-triazolo[4,3-a]pyridines

Methods for the synthesis of (pyridinyl)-1,2,4-triazolo4,3-a]pyridines were developed. The principal route to the required intermediate 2-chloropyridines was based on rearrangements of mono N-oxides of 2,2′-bipyridine, 2,3′-bipyridine, 3,3′-bipyridine, 2,4′-bipyridine and 4,4′-bipyridine with phosphorus oxychloride. Reaction of 3,3′-bipyridine 1-oxide or 2,2′-bipyridine 1-oxide with phosphorus oxychloride gave mixtures of chloro isomers. Reaction with acetic anhydride, 3,3′-bipyridine 1-oxide and 2,2′-bipyridine 1-oxide gave exclusively 3,3′-bipyridine]-2(1H)-one and 2,2′-bipyridine]-6(1H)-one, respectively. 1,2,4-Triazolo4,3-a]pyridines with pyridinyl groups at the 5,6,7 and 8 positions were synthesized.