Carbon‐13 NMR investigation of the protonation and quaternization of azoloazines with a bridgehead nitrogen

Carbon‐13 nmr techniques have been employed to study imidazo[1,2‐a]pyridine, imidazo‐[ 1,2‐b]pyridazine, s‐triazolo[4,3‐b]pyridazine, and s‐triazolo[ 1,5‐b]pyridazine and their N‐1 quaternized derivatives. The data on quaternized derivatives have been analyzed to determine the tautomeric structures possible in the protonated derivatives. The data suggest that protonation at the bridgehead nitrogen does not occur in these compounds and, of the possible tautomerie forms, the N‐1 tautomer predominates.