Methanol → 4-Bromo-2-methoxybenzonitrile

HRID 1443334Notes

Reaction equation

HRID 1443334 reaction equation
[Br:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4](F)[CH:3]=1.CO.[C:13](=O)([O-])[O-:14].[K+].[K+].C(Cl)Cl>CN(C=O)C.O.CCOCC>[Br:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([O:14][CH3:13])[CH:3]=1

Participants

8

Reactant 4

HCID 887MethanolHCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 7360294-Bromo-2-fluorobenzonitrile

Product 1

HCID 223467024-Bromo-2-methoxybenzonitrileYield 95.6%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
55 °C

Procedure

A mixture of 4-bromo-2-fluoro-benzonitrile (15.0 g, 75.0 mmol), methanol (30.4 mL, 350 mmol) and potassium carbonate (31.1 g, 225 mmol) in DMF (150 mL) was stirred under argon at 55° C. overnight. At this point TLC (100% methylene chloride) revealed no starting material, and the reaction mixture was poured into ether (300 mL) and water (150 mL). The layers were separated, and the organic layer was washed with water (150 mL) and brine (50 mL), dried over Mg2SO4, filtrated, and concentrated under reduced pressure, providing (15.2 g, 95.5%) of 4-bromo-2-methoxy-benzonitrile as a white solid. 1H-NMR (CDCl3) δ 7.41 (d, J=8.1 Hz, 1H), 7.16 (dd, J=8.1, 1.6 Hz, 1H), 7.13 (d, J=1.6 Hz, 1H), 3.93 (s, 3H); MS GC-MS (M+=211; RT=6.15 min).

Workup

  1. customThe layers were separated
  2. washthe organic layer was washed with water (150 mL) and brine (50 mL)
  3. dry with materialdried over Mg2SO4
  4. filtrationfiltrated
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-de891202e06546e6b846e61b0149ba59
Source dataset
uspto-grants-2010_02
Patent number
US07659412B2

Reaction notes

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