Methanol → Methyl 3-bromo-5-(methylthio)benzoate
Reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([S:11][CH3:12])[CH:10]=1)[C:5]([OH:7])=[O:6].[C:13](Cl)(=O)C(Cl)=O.CO.C(N(CC)C(C)C)(C)C>CN(C=O)C.C(Cl)Cl>[Br:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([S:11][CH3:12])[CH:10]=1)[C:5]([O:7][CH3:13])=[O:6]Participants
7
Procedure
To a stirred mixture of 3-bromo-5-methylsulfanyl-benzoic acid (2.2 g, 8.9 mmol), methylene chloride (100 mL), and DMF (5 drops) at 0° C. was added oxalyl chloride (1.0 mL, 12 mmol). The mixture was slowly warmed to room temperature and stirred at room temperature overnight. Methanol (5.0 mL, 120 mmol) and N,N-diisopropylethylamine (5.0 mL, 29 mmol) were added and the mixture was stirred at room temperature for 3 h and then concentrated. The residue was purified by silica gel column (0-50% EtOAc/hexane) to yield an oil. 1H NMR (400 MHz, CDCl3): δ 7.91 (t, 1H, J=1.6 Hz), 7.81 (t, 1H, J=1.6 Hz), 7.52 (t, 1H, J=1.6 Hz), 3.92 (s, 3H), 2.52 (s, 3H).
Workup
- stirringthe mixture was stirred at room temperature for 3 h
- concentrationconcentrated
- customThe residue was purified by silica gel column (0-50% EtOAc/hexane)
- customto yield an oil
Sources & evidence
- ORD record
- ord-88b435adbc9b49cd836a86d29a960494
- Source dataset
- uspto-grants-2015_02
- Patent number
- US08946439B2
Reaction notes
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