Stannous Chloride → 4-Chloro-3-(pyrid-3-yl)aniline

Reaction equation

[Sn](Cl)Cl.[Cl:4][C:5]1[CH:10]=[CH:9][C:8]([N+:11]([O-])=O)=[CH:7][C:6]=1[C:14]1[CH:15]=[N:16][CH:17]=[CH:18][CH:19]=1>C(O)C.O1CCOCC1>[Cl:4][C:5]1[CH:10]=[CH:9][C:8]([NH2:11])=[CH:7][C:6]=1[C:14]1[CH:15]=[N:16][CH:17]=[CH:18][CH:19]=1

Participants

Procedure

Tin(II) chloride (11.87 g, 62.6 mmol) was added portionwise over 5 min to a stirred mixture of 3-(2-chloro-5-nitrophenyl)pyridine (3.53 g, 15.1 mmol) in ethanol (100 ml) and 1,4-dioxane (100 ml) at 0° C. The mixture was then stirred overnight, gradually warming to room temperature, and then concentrated under reduced pressure. 20% Aqueous ammonia solution (200 ml) and ethanol (300 ml) were added and again the mixture concentrated under reduced pressure. Ethyl acetate (300 ml) was added and the mixture heated to reflux, the solids were filtered off and the process repeated twice more. The combined organic filtrates were concentrated under reduced pressure to yield the title compound (2.69 g, 87%): 1H NMR (360 MHz, CDCl3) δ 6.65-6.70 (2H, m), 7.26 (1H, dt, J 8.5, 1.1 Hz), 7.33 (1H, dd, J 7.8, 4.8 Hz), 7.77 (1H, dt, J 7.8, 1.9 Hz), 8.59 (1H, dd, J 4.8, 1.6 Hz), 8.66 (1H, d, J 1.8 Hz); MS (ES+) m/z 205, 207 (3:1) [M+H]+.