N-bromobutanimide → Methyl 2-(bromomethyl)-3-(trifluoromethyl)benzoate
Reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([C:10]([F:13])([F:12])[F:11])[C:5]=1[CH3:14].[Br:16]N1C(=O)CCC1=O.C(OCC)(=O)C.CCCCCC>C1C=CC=CC=1.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([C:10]([F:12])([F:11])[F:13])[C:5]=1[CH2:14][Br:16]Participants
Procedure
To a solution of 2-methyl-3-trifluoromethyl-benzoic acid methyl ester (0.95 g, 4.35 mmol) in benzene (10 mL) was added N-bromosuccinimide (0.77 g, 4.33 g) and benzoyl peroxide (0.052 g, 0.21 mmol) and the resulting mixture heated to reflux for 4 h, cooled and stirred at room temperature for 48 h. The mixture was filtered, the filter cake washed with diethyl ether and the filtrate washed with a 1 N sodium thiosulfate solution (10 mL), brine and dried over magnesium sulfate. The mixture was filtered and evaporated and the residue purified via automated flash chromatography (Analogix, SF25-80 g column, 5→10% ethyl acetate/hexane gradient) to give 2-bromomethyl-3-trifluoromethyl-benzoic acid methyl ester (1.04 g, 3.50 mmol, 81%) as an off white solid; 1H NMR (300 MHz, DMSO-d6) δ ppm 3.72-4.16 (m, 3H), 5.03 (s, 2H), 7.47-8.32 (m, 3H).
Workup
- temperaturethe resulting mixture heated
- temperatureto reflux for 4 h
- temperaturecooled
- filtrationThe mixture was filtered
- washthe filter cake washed with diethyl ether
- washthe filtrate washed with a 1 N sodium thiosulfate solution (10 mL), brine
- dry with materialdried over magnesium sulfate
- filtrationThe mixture was filtered
- customevaporated
- customthe residue purified
Sources & evidence
- ORD record
- ord-3fcb17b21f68425db4386766e9228ac0
- Source dataset
- uspto-grants-2014_04
- Patent number
- US08697705B2
Reaction notes
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