[3-fluoro-4-(1H-pyrazol-1-yl)phenyl]amine → 2-Bromo-5-fluoro-4-(1H-pyrazol-1-yl)benzenamine

HRID 586334Notes

Reaction equation

HRID 586334 reaction equation
[F:1][C:2]1[C:3]([N:9]2[CH:13]=[CH:12][CH:11]=[N:10]2)=[CH:4][CH:5]=[C:6]([NH2:8])[CH:7]=1.[Br-:14].[Br-].[Br-].[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1>O1CCCC1.C(OCC)C>[Br:14][C:5]1[CH:4]=[C:3]([N:9]2[CH:13]=[CH:12][CH:11]=[N:10]2)[C:2]([F:1])=[CH:7][C:6]=1[NH2:8]

Participants

5

Reactant 2

HCID 10725981[3-fluoro-4-(1H-pyrazol-1-yl)phenyl]amineHCID 21124087Pyridiniumtribromide

Product 1

HCID 223295562-Bromo-5-fluoro-4-(1H-pyrazol-1-yl)benzenamine

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 5-fluoro-4-(pyrazol-1-yl)phenylamine (2.56 g, 14.5 mmol) in tetrahydrofuran (50 ml) was added dropwise a solution of pyridinium tribromide (5.09 g, 15.9 mmol) in tetrahydrofuran (50 ml). The mixture was stirred for 1 h at room temperature then diluted with diethyl ether (250 ml). After stirring for a further 30 min the precipitate was filtered and washed with diethyl ether (50 ml×2). The white solid was dissolved in water (200 ml) and extracted with ethyl acetate (100 ml×3). The combined organic phases were dried over magnesium sulphate, filtered and the solvent removed to leave an orange oil. Purification by chromatography (silica gel, CH2Cl2) gave 2-bromo-5-fluoro-4(pyrazol-1-yl)phenylamine as a white solid: MS (ES+) m/z 256 and 258 [M+H]+.

Workup

  1. stirringAfter stirring for a further 30 min the precipitate
  2. filtrationwas filtered
  3. washwashed with diethyl ether (50 ml×2)
  4. dissolutionThe white solid was dissolved in water (200 ml)
  5. extractionextracted with ethyl acetate (100 ml×3)
  6. dry with materialThe combined organic phases were dried over magnesium sulphate
  7. filtrationfiltered
  8. customthe solvent removed
  9. customto leave an orange oil
  10. customPurification by chromatography (silica gel, CH2Cl2)

Sources & evidence

ORD record
ord-c4aad5e859c34d37ae49607307fb9a2a
Source dataset
uspto-grants-2005_08
Patent number
US06936608B2

Reaction notes

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