Dichloromethane → 5-Bromo-4-(trifluoromethyl)pyridin-2-amine

HRID 1512088Notes

Reaction equation

HRID 1512088 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[CH:4][N:3]=1.[Br:12]N1C(=O)CCC1=O.C(Cl)Cl.[OH-].[Na+]>C(Cl)(Cl)Cl>[Br:12][C:5]1[C:6]([C:8]([F:9])([F:11])[F:10])=[CH:7][C:2]([NH2:1])=[N:3][CH:4]=1

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 14798Sodium HydroxideHCID 67184N-bromobutanimideHCID 27783152-Amino-4-(trifluoromethyl)pyridine

Product 1

HCID 288753485-Bromo-4-(trifluoromethyl)pyridin-2-amineYield 80.2%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To a solution of 2-amino-4-trifluoromethylpyridine (10.0 g, 62.1 mmol) in chloroform (200 mL) was added N-bromosuccinimide (12.0 g, 67.4 mmol). The solution was stirred in the dark for 2 hours, at which time it was added to CH2Cl2 (200 mL) and 1N NaOH (200 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 (0-5% EtOAc/CH2Cl2) yielding 12.0 g (80%) of 5-bromo-4-(trifluoromethyl)-2-pyridylamine LCMS (m/z): 241/243 (MH+). 1H NMR (CDCl3): δ 8.28 (s, 1H), 6.77 (s, 1H), 4.78 (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 (0-5% EtOAc/CH2Cl2)

Sources & evidence

ORD record
ord-22b3ac87fd0f4254ab58fe3a1685a46e
Source dataset
uspto-grants-2012_07
Patent number
US08217035B2

Reaction notes

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