3-Bromo-5-chloropyridin-2-amine → 3-Bromo-5-chloropyridin-2-ol

HRID 974226Notes

Reaction equation

HRID 974226 reaction equation
N[C:2]1[C:7]([Br:8])=[CH:6][C:5]([Cl:9])=[CH:4][N:3]=1.N([O-])=[O:11].[Na+]>O.Cl>[Br:8][C:7]1[C:2](=[O:11])[NH:3][CH:4]=[C:5]([Cl:9])[CH:6]=1

Participants

5

Reactant 2

HCID 27639713-Bromo-5-chloropyridin-2-amineHCID 23668193Sodium Nitrite

Product 1

HCID 27267913-Bromo-5-chloropyridin-2-olYield 74.8%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent2×

Procedure

To a cooled (0° C.) solution of 2-amino-3-bromo-5-chloropyridine (100 g, 0.482 mol) in water (815 mL) and concentrated HCl (130 mL) was added a solution of sodium nitrite (33.26 g, 0.482 mol) in water (272 mL). The resulting suspension was allowed to warm to room temperature and stir for 18 hours, at which point the solids were filtered, washed with carbon tetrachloride (2×50 mL), and dried in a vacuum oven (40° C.) to yield 75.1 g (74.8%) of gray-yellow solid, m.p. 170-173° C.: IR(mineral oil (Nujol (trademark)) 3111, 3041, 2947, 2919, 2850, 2722, 1814, 1696, 1663, 1643, 1585, 1527, 1462, 1377, 1302, 1234, 1171, 1153, 1123, 1106, 1040, 1031, 917, 896, 876, 839, 747, 726, 644, 635, 561, 539, 523, 410, 251, 235, 225, 220 cm-1 ; 1H NMR (300 MHz, D6 -DMSO) δ 7.72 (d, 1H, J=2.2 Hz), 8.08 (d, 1H, J=2.2 Hz), 12.41 (br s, 1H); 13C NMR (DMSO) δ 110.88, 115.35, 134.08, 142.64, 157.56; exact mass calculated for C5H3NBrClO=206.9086. High resolution mass spec. 206.9093.

Workup

  1. filtrationwere filtered
  2. washwashed with carbon tetrachloride (2×50 mL)
  3. customdried in a vacuum oven (40° C.)

Sources & evidence

ORD record
ord-b83914d325ef4486a6a0ea1cf4ae5ba7
Source dataset
uspto-grants-1991_11
Patent number
US05068333

Reaction notes

Loading…