Dichloromethane → 5-Bromo-6-fluoropyridin-2-amine

HRID 1043766Notes

Reaction equation

HRID 1043766 reaction equation
[F:1][C:2]1[N:7]=[C:6]([NH2:8])[CH:5]=[CH:4][CH:3]=1.[Br:9]N1C(=O)CCC1=O.C(Cl)Cl.[OH-].[Na+]>C(Cl)(Cl)Cl>[Br:9][C:3]1[CH:4]=[CH:5][C:6]([NH2:8])=[N:7][C:2]=1[F:1]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 14798Sodium HydroxideHCID 67184N-bromobutanimideHCID 27613996-Fluoropyridin-2-amine

Product 1

HCID 534184365-Bromo-6-fluoropyridin-2-amineYield 22.6%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To a solution of 6-fluoro-2-pyridylamine (1.0 g, 8.93 mmol) in chloroform (55 mL) was added N-bromosuccinimide (1.59 g, 8.93 mmol). The solution was stirred in the dark for 15 hours, at which time it was added to CH2Cl2 (200 mL) and 1N NaOH (50 mL) Upon mixing, the layers were separated and the organic layer was washed with NaCl(sat.) (50 mL), dried over Na2SO4, filtered and concentrated. The crude material was purified by SiO2 chromatography (25% EtOAc/hexanes) yielding 5-bromo-6-fluoro-2-pyridylamine (386 mg, 22%). LCMS (m/z): 190.9/192.9 (MH+); 1H NMR (CDCl3): δ 7.59 (t, J=8.7 Hz, 1H), 6.25 (dd, J=8.1, 1.2 Hz, 1H), 4.58 (bs, 1H).

Workup

  1. additionUpon mixing
  2. customthe layers were separated
  3. washthe organic layer was washed with NaCl(sat.) (50 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude material was purified by SiO2 chromatography (25% EtOAc/hexanes)

Sources & evidence

ORD record
ord-062d63c3335d4f019096c0bbf8670f1c
Source dataset
uspto-grants-2013_10
Patent number
US08563549B2

Reaction notes

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