Ammonia → 6-Chloro-3-nitropyridin-2-ylamine

Reaction equation

Cl[C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[C:4]([Cl:11])[N:3]=1.CCO.O.[NH3:16]>>[Cl:11][C:4]1[N:3]=[C:2]([NH2:16])[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=1

Participants

Reactant 4

HCID 222Ammonia

HCID 702Ethanol

HCID 962Water

HCID 852392,6-Dichloro-3-nitropyridine

Product 1

HCID 27240356-Chloro-3-nitropyridin-2-ylamineYield 89%

Procedure

2,6-Dichloro-3-nitropyridine 90 (10.0 g, 51.8 mmol) was dissolved in 37 ml of a 7N solution of NH3 in EtOH (0.26 mol, 5.0 eqv) and the solution was stirred at rt for 24 h. H2O (40 ml) was added and the resulting mixture was filtered to collect the crude yellow product. The solid material was dissolved in CH2Cl2 and then extracted with a 1N HCl solution. The aqueous extracts were combined and then neutralized with NaHCO3 before being re-extracted with CH2Cl2. The organic fractions were combined, dried (MgSO4), filtered, and concentrated in vacuo to yield 8.0 g of a yellow solid (89%): 1H NMR (400 MHz, d6-DMSO) d 6.77 (d, J=8.8 Hz, 1H), 8.27 (s, 2H), 8.39 (d, J=8.4 Hz, 1H); 13C NMR (125 MHz, d6-DMSO) d 111.89, 126.02, 138.28, 153.36, 154.88; HRMS (EI) Calcd for C5H4ClN3O2: 172.9997. Found 172.9996.