Sulfuric Acid → 3-Azidopyridine

Participants

Reaction Conditions

Reaction Steps

3-Aminopyridine (18.89 g, 0.20 mol) was added to a warm (55° C.) solution of 36 ml of concentrated sulfuric acid in 210 ml of water. The mixture was stirred for five minutes and was then cooled to 5° C. and a solution of 16.66 g (0.24 mol) of sodium nitrite in 140 ml of water was added dropwise, keeping the temperature below 6° C. The mixture was left to stir for 20 minutes. Urea (2.4 g, 0.04 mol) was added and the mixture was again left to stir at 5° C. for 20 minutes. A solution of 15.60 g (0.24 mol) of sodium azide in 150 ml of water was added, keeping the temperature below 10° C. Nitrogen was immediately evolved. The mixture was stirred at ambient temperature for 1.5 hours after the addition was complete and was then neutralized to pH 6-7 with sodium bicarbonate and extracted with ether. The ether extract was dried over magnesium sulfate and stripped of solvent to yield 21.5 g (89 percent of theory) of dark oil. NMR (CDCl3): δ8.58 (m, 2H) δ7.47 (m, 2H).

Provenance & Evidence