Methyl Acrylate → Methyl 3-bromo-4-[(1E)-3-methoxy-3-oxoprop-1-en-1-yl]benzoate

Temperature

50 °C

A mixture of methyl 3-bromo-4-iodobenzoate (5.9 g, 17 mmol), methyl acrylate (2.01 mL, 22.3 mmol), tetra-N-butylammonium chloride (4.8 g, 17 mmol), palladium acetate (80 mg, 0.3 mmol) and finely ground potassium carbonate (5.98 g, 43.3 mmol) in N,N-dimethylformamide (21 mL) was stirred at 50° C. for 20 h. The reaction mixture was cooled to room temperature. Ethyl acetate (200 mL) and brine (50 mL) were added, and the mixture was filtered under suction. The filtrate was collected, and aqueous layer was extracted with ethyl acetate twice. The combined organic layers were dried over NaSO4, filtered, and concentrated. The product was crashed out after concentration, filtered and washed with ethyl acetate to give product. The remained residue was purified with silica gel chromatography (10% ethyl acetate/hexanes) to provide white solid (3.5 g, 67%). 1H NMR (400 MHz, CDCl3): δ 8.27 (d, J=1.7 Hz, 1H), 8.04 (d, J=16.0 Hz, 1H), 7.98 (m, 1H), 7.65 (d, J=8.2 Hz, 1H), 6.46 (d, J=15.8 Hz, 1H), 3.94 (s, 3H), 3.84 (s, 3H). LCMS found for C12H12BrO4 (M+H)+: m/z=299, 301.

1. temperatureThe reaction mixture was cooled to room temperature
2. filtrationthe mixture was filtered under suction
3. customThe filtrate was collected
4. extractionaqueous layer was extracted with ethyl acetate twice
5. dry with materialThe combined organic layers were dried over NaSO4
6. filtrationfiltered
7. concentrationconcentrated
8. concentrationafter concentration
9. filtrationfiltered
10. washwashed with ethyl acetate
11. customto give product
12. customThe remained residue was purified with silica gel chromatography (10% ethyl acetate/hexanes)

ORD record

ord-93026ea211764a62b211b9c889bae89f

Source dataset

uspto-grants-2006_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07141596B2