Benzoic acid, 4-bromo-3-methoxy-2-methyl-, methyl ester → Benzoic acid, 4-cyano-3-methoxy-2-methyl-, methyl ester
Reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([CH3:12])[C:3]=1[O:13][CH3:14].[Cu][C:16]#[N:17]>CN(C)C=O>[C:16]([C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([CH3:12])[C:3]=1[O:13][CH3:14])#[N:17]Participants
Conditions
- Temperature
- 150 °C
Procedure
To a sealed tube vessel was added methyl 4-bromo-2-methyl-3-(methyloxy)benzoate (280 mg, 1.08 mmol), copper (I) cyanide (97 mg, 1.08 mmol) and dimethylformamide (2 mL). The mixture was heated at 150° C. for 24 hours, then was cooled to room temperature and filtered through a pad of Celite. After washing the Celite with ethyl acetate, the combined filtrate was washed with 5% aqueous lithium chloride, and brine, then dried over anhydrous sodium sulfate. Filtration and concentration afforded a brown residue that was purified by silica gel column chromatography. Eluting with 10% ethyl acetate in hexane, purified fractions were pooled and concentrated to afford 150 mg, 0.73 mmol (68%) of methyl 4-cyano-2-methyl-3-(methyloxy)benzoate. 1H NMR (400 MHz, CDCl3): 7.61 (d, 1H), 7.47 (d, 1H), 3.99 (s, 3H), 3.93 (s, 3H), 2.49 (s, 3H). MS (EI) for C11H11NO3: 206 (MH+).
Workup
- temperaturewas cooled to room temperature
- filtrationfiltered through a pad of Celite
- washAfter washing the Celite with ethyl acetate
- washthe combined filtrate was washed with 5% aqueous lithium chloride, and brine
- dry with materialdried over anhydrous sodium sulfate
- filtrationFiltration and concentration
- customafforded a brown residue that
- customwas purified by silica gel column chromatography
- washEluting with 10% ethyl acetate in hexane
- custompurified fractions
- concentrationconcentrated
Sources & evidence
- ORD record
- ord-40035cb96b3e4e4aa2e9b9230231905c
- Source dataset
- uspto-grants-2011_09
- Patent number
- US08012956B2
Reaction notes
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