Carbon Tetrachloride → Methyl 2-bromo-2-(4-nitrophenyl)acetate
Reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([CH2:10][C:11]([O:13][CH3:14])=[O:12])=[CH:6][CH:5]=1)([O-:3])=[O:2].C(Cl)(Cl)(Cl)Cl.[Br:20]N1C(=O)CCC1=O.CC(N=NC(C#N)(C)C)(C#N)C>CCCCCCC>[Br:20][CH:10]([C:7]1[CH:6]=[CH:5][C:4]([N+:1]([O-:3])=[O:2])=[CH:9][CH:8]=1)[C:11]([O:13][CH3:14])=[O:12]Participants
Procedure
A 1-L single-neck round-bottomed flask equipped with a magnetic stirrer and reflux condenser was charged with 1 (10.6 g, 54.1 mmol), carbon tetrachloride (120 mL), N-bromosuccinimide (10.7 g, 59.9 mmol) and azobisisobutylonitrile (275 mg, 1.67 mmol), and the reaction mixture was heated at reflux for 18 h. After this time the reaction was cooled to room temperature and poured into heptane (120 mL). The resulting suspension was filtered and the filter cake washed with heptane (40 mL). The filtrate was concentrated under reduced pressure and the resulting residue was subjected to flash chromatography to afford 2 in 72% yield (10.7 g) as a clear oil: 1H NMR (500 MHz, CDCl3) δ 8.23 (d, 2H, J=9 Hz), 7.74 (d, 2H, J=9.0 Hz), 5.40 (s, 1H), 3.82 (s, 3H); MS (ESI−) m/z 272 (M−H). Reference: Tetrahedron 2002, 58, 10113.
Workup
- customA 1-L single-neck round-bottomed flask equipped with a magnetic stirrer
- temperaturereflux condenser
- temperaturethe reaction mixture was heated
- temperatureat reflux for 18 h
- filtrationThe resulting suspension was filtered
- washthe filter cake washed with heptane (40 mL)
- concentrationThe filtrate was concentrated under reduced pressure
- customto afford 2 in 72% yield (10.7 g) as a clear oil
Sources & evidence
- ORD record
- ord-649b64581f2141de802fbe8a0b97199e
- Source dataset
- uspto-grants-2012_08
- Patent number
- US08247550B2
Reaction notes
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