N-bromobutanimide → Methyl 3-(bromomethyl)thiophene-2-carboxylate
Reaction equation
[CH3:1][C:2]1[CH:6]=[CH:5][S:4][C:3]=1[C:7]([O:9][CH3:10])=[O:8].[Br:11]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl>[Br:11][CH2:1][C:2]1[CH:6]=[CH:5][S:4][C:3]=1[C:7]([O:9][CH3:10])=[O:8]Participants
Reactant 2
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 90 °C
Procedure
To a solution of methyl 3-methylthiophene-2-carboxylate (10.0 g, 64.0 mmol) in CCl4 (100 mL) was added AlBN (180 mg, 1.1 mmol) and N-bromosuccinimide (11.4 g, 64.0 mmol). The reaction mixture was refluxed for 10 min, and then an additional portion of AlBN (460 mg, 2.8 mmol) was added. This reaction was heated overnight at 90° C. under a reflux condenser. At completion, the reaction was filtered over a short plug of silica gel (100% DCM eluent). The filtrate was concentrated and purified by flash chromatography over silica gel (2% EtOAc/hexane eluent) to afford methyl 3-(bromomethyl)thiophene-2-carboxylate (9.5 g, 63% yield) as a white solid. 1H NMR (400 MHz, METHANOL-d4) δ ppm 7.66 (d, J=5.0 Hz, 1H), 7.23 (d, J=5.0 Hz, 1H), 4.95 (s, 2H), 3.89 (s, 3H); MS (EI) m/z=236.1 [M+1]+.
Workup
- temperatureThe reaction mixture was refluxed for 10 min
- filtrationAt completion, the reaction was filtered over a short plug of silica gel (100% DCM eluent)
- concentrationThe filtrate was concentrated
- custompurified by flash chromatography over silica gel (2% EtOAc/hexane eluent)
Sources & evidence
- ORD record
- ord-fb1a7e553f7343d4a6356a3b19d70ed2
- Source dataset
- uspto-grants-2013_05
- Patent number
- US08440652B2
Reaction notes
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