Methanol → 4-Bromo-2-methoxybenzonitrile

HRID 1717648Notes

Reaction equation

HRID 1717648 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-37c03fc7972948809d4e11f747a23dec
Source dataset
uspto-grants-2010_09
Patent number
US07803956B2

Reaction notes

Loading…