Methanol → Methyl 2-bromo-5-methylbenzoate

To a solution of 2-bromo-5-methylbenzoic acid (215 mg, 1.0 mmol) in DCM (4 mL) and DMF (1 drop) at 0° C. was slowly added oxalyl chloride (0.13 mL, 1.5 mmol). The reaction mixture was stirred at rt for 1 h and to it was added additional oxalyl chloride (0.13 mL, 1.5 mmol). The reaction mixture was stirred for 1 h, added with MeOH (2 mL) and stirred for 6 h. The mixture was treated with Na2CO3 to pH of 9 and extracted with DCM (2×10 mL). The combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography over silica gel eluted with PE-EA (15:1) to give methyl 2-bromo-5-methylbenzoate (210 mg; yield 92%) as colorless oil. 1H NMR (400 MHz, CDCl3): δ 7.60 (d, J=1.6 Hz, 1 H), 7.53 (d, J=8.8 Hz, 1 H), 7.15 (q, J=3.2 Hz, 1H), 3.92 (s, 3 H), 2.33 (s, 3 H) ppm.

1. customat 0° C.
2. stirringThe reaction mixture was stirred for 1 h
3. stirringstirred for 6 h
4. extractionextracted with DCM (2×10 mL)
5. washThe combined organic layers were washed with brine
6. dry with materialdried over Na2SO4
7. filtrationfiltered
8. concentrationconcentrated under reduced pressure
9. customThe residue was purified by column chromatography over silica gel
10. washeluted with PE-EA (15:1)

ORD record

ord-1af6c0e441b84788a2aea18515a02ad9

Source dataset

uspto-grants-2014_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08853186B2