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

HRID 2184059Notes

Reaction equation

HRID 2184059 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([NH2:13])[CH:5]=[CH:6][C:7]=1[N:8]1[CH:12]=[CH:11][CH:10]=[N:9]1.[Br-:14].[Br-].[Br-].[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1>O1CCCC1.CCOCC>[Br:14][C:5]1[CH:6]=[C:7]([N:8]2[CH:12]=[CH:11][CH:10]=[N:9]2)[C:2]([F:1])=[CH:3][C:4]=1[NH2:13]

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 3-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 ether (250 ml). After stirring for a further 30 min the precipitate was filtered and washed with 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 on silica gel eluting with dichloromethane gave 2-bromo-5-fluoro-4-(pyrazol-1-yl)phenylamine as a white solid: m/z (ES+) 256 and 258 (M++H).

Workup

  1. stirringAfter stirring for a further 30 min the precipitate
  2. filtrationwas filtered
  3. washwashed with 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 on silica gel eluting with dichloromethane

Sources & evidence

ORD record
ord-74acf7d9084446ae86e9cd7725be222f
Source dataset
uspto-grants-2005_05
Patent number
US06900215B2

Reaction notes

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