Dichloromethane → 2-Amino-5-bromo-4-chloropyridine

HRID 1043761Notes

Reaction equation

HRID 1043761 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([NH2:8])[CH:3]=1.[Br:9]N1C(=O)CCC1=O.C(Cl)Cl.[OH-].[Na+]>C(Cl)(Cl)Cl>[Br:9][C:7]1[C:2]([Cl:1])=[CH:3][C:4]([NH2:8])=[N:5][CH:6]=1

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 14798Sodium HydroxideHCID 67184N-bromobutanimideHCID 5818662-Amino-4-chloropyridine

Product 1

HCID 441818122-Amino-5-bromo-4-chloropyridineYield 38%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To a solution of 4-chloro-2-pyridylamine (6.0 g, 46.7 mmol) in chloroform (180 mL) was added N-bromosuccinimide (8.3 g, 46.7 mmol). The solution was stirred in the dark for 2 hours, at which time it was added to CH2Cl2 (800 mL) and 1N NaOH (100 mL). Upon mixing, the layers were separated and the organic layer was washed with NaCl(sat.) (100 mL), dried over Na2SO4, filtered and concentrated. The crude material was purified by SiO2 chromatography (25-35% EtOAc/hexanes) yielding 3.63 g (38%) of 5-bromo-4-chloro-2-pyridylamine. LCMS (m/z): 206.9/208.9 (MH+). 1H NMR (CDCl3): δ 8.18 (s, 1H), 6.62 (s, 1H), 4.52 (bs, 2H).

Workup

  1. additionUpon mixing
  2. customthe layers were separated
  3. washthe organic layer was washed with NaCl(sat.) (100 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude material was purified by SiO2 chromatography (25-35% EtOAc/hexanes)

Sources & evidence

ORD record
ord-5608211cab77488a87f2abc2a3a439d4
Source dataset
uspto-grants-2013_10
Patent number
US08563549B2

Reaction notes

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