Dimethylformamide → Methyl 5-bromo-4-cyano-2-hydroxy-3-methylbenzoate

To a solution of 5-bromo-4-cyano-2-hydroxy-3-methylbenzoic acid (7.40 g) in dichloromethane (70.0 mL) were added oxalyl chloride (3.91 g) and DMF (0.20 mL) under ice-cooling, and the mixture was stirred for 3 hr. The reaction mixture was concentrated under reduced pressure, and the residue was diluted with THF. To this mixture was added dropwise a solution of triethylamine (5.66 g) in methanol (50.0 mL) under ice-cooling, and the mixture was stirred for 20 min. The reaction mixture was poured into 1N hydrochloric acid, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/petroleum ether) to give the title compound (4.20 g).

1. temperaturecooling
2. concentrationThe reaction mixture was concentrated under reduced pressure
3. additionthe residue was diluted with THF
4. additionTo this mixture was added dropwise a solution of triethylamine (5.66 g) in methanol (50.0 mL) under ice-
5. temperaturecooling
6. stirringthe mixture was stirred for 20 min
7. additionThe reaction mixture was poured into 1N hydrochloric acid
8. extractionthe mixture was extracted with ethyl acetate
9. dry with materialThe organic layer was dried over anhydrous sodium sulfate
10. customthe solvent was evaporated under reduced pressure
11. customThe residue was purified by silica gel column chromatography (ethyl acetate/petroleum ether)

ORD record

ord-ebcdef67a2564d7f97e5dc0f853b3c0c

Source dataset

uspto-grants-2016_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09315458B2