Uses
Methyl 4-bromo-3-methylbenzoate may be used in the preparation of:
- 4-bromo-3-vinylbenzoic acid
- 4-bromo-3-(methylphenyl)methanol
- methyl (E)-4-bromo-3-[(phenylmethoxyimino)methyl]benzoate
It may be used as a starting material in the total synthesis of (-)-martinellic acid.
General Description
Methyl 4-bromo-3-methylbenzoate, an aromatic ester, undergoes Suzuki coupling with 2-chloroboronic acid to afford the corresponding biaryl.
Synthesis
To a concentrated solution of 4-bromo-3-methylbenzoic acid (3 g, 13.19 mmol) in methanol (15 ml) was added concentrated sulfuric acid (catalytic amount). The reaction mixture was heated to reflux for 14 hours and subsequently cooled to 0°C. The reaction mixture was neutralized with saturated sodium bicarbonate solution and the precipitated solid product was collected by filtration. The crude product was purified by silica gel column chromatography to afford methyl 4-bromo-3-methylbenzoate (3.1 g, 97% yield) as a white solid.
References
[1] Patent: US2011/71150, 2011, A1. Location in patent: Page/Page column 33
[2] Angewandte Chemie - International Edition, 2008, vol. 47, # 44, p. 8482 - 8486
[3] Patent: WO2006/110173, 2006, A2. Location in patent: Page/Page column 78
[4] Chemical Communications, 2018, vol. 54, # 65, p. 9051 - 9054
[5] Patent: US2013/131016, 2013, A1. Location in patent: Paragraph 0189
