N-bromobutanimide → 4-Amino-3-bromo-5-fluorobenzonitrile

HRID 1848195Notes

Reaction equation

HRID 1848195 reaction equation
[NH2:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[F:10].[Br:11]N1C(=O)CCC1=O>C(Cl)Cl>[NH2:1][C:2]1[C:3]([F:10])=[CH:4][C:5]([C:6]#[N:7])=[CH:8][C:9]=1[Br:11]

Participants

4

Reactant 2

HCID 67184N-bromobutanimideHCID 27564314-Amino-3-fluorobenzonitrile

Product 1

HCID 288206604-Amino-3-bromo-5-fluorobenzonitrileYield 81%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred mixture of 4-amino-3-fluorobenzonitrile (5 g, 37 mmol) in anhydrous CH2Cl2 (40 mL) under Ar at rt was added dropwise N-bromosuccinimide (6.5 g, 37 mmol). After 15 h, the mixture was concentrated under reduced pressure. The residue was purified by silica gel flash chromatography eluting with a gradient of 100% hexanes to 50% EtOAc in hexanes to afford 4-amino-3-bromo-5-fluorobenzonitrile (6.4 g, 81%) as a tan solid. 1H NMR (500 MHz, DMSO-d6) δ 7.76 (s, 1H), 7.62 (dd, J=1.5, 11.1 Hz, 1H), 6.44 (s, 2H); LCMS (ESI) m/z 214, 216 (M+H)+.

Workup

  1. concentrationthe mixture was concentrated under reduced pressure
  2. customThe residue was purified by silica gel flash chromatography
  3. washeluting with a gradient of 100% hexanes to 50% EtOAc in hexanes

Sources & evidence

ORD record
ord-4529fac0d7e9466bb0e22238fb295de9
Source dataset
uspto-grants-2015_02
Patent number
US08952058B2

Reaction notes

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