4-Bromoaniline → Ethyl 3-(4-bromophenylamino)-2-(methylsulfonyl)acrylate
Reaction equation
[CH3:1][S:2]([CH2:5][C:6]([O:8][CH2:9][CH3:10])=[O:7])(=[O:4])=[O:3].[CH:11](OCC)(OCC)OCC.C(OC(=O)C)(=O)C.[Br:28][C:29]1[CH:35]=[CH:34][C:32]([NH2:33])=[CH:31][CH:30]=1>>[Br:28][C:29]1[CH:35]=[CH:34][C:32]([NH:33][CH:11]=[C:5]([S:2]([CH3:1])(=[O:4])=[O:3])[C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:31][CH:30]=1Participants
5
Conditions
- Temperature
- 130 °C
Procedure
A mixture of ethyl 2-(methylsulfonyl)acetate (1.9 g, 11.4 mmol), triethyl orthoformate (5.64 mL, 34.2 mmol), and acetic anhydride (5 mL) were heated at 130° C. for 5 h with a Dean Stark trap. The reaction was cooled, 4-bromoaniline (3.1 g, 18.0 mmol) was added and the reaction mixture was heated at 150° C. for 2 h. The reaction mixture was cooled, concentrated and the residue was purified by column chromatography to afford the desire product (1.08 g, 27% over 2 steps) as a tan solid: 1H NMR (300 MHz, CDCl3) δ 10.58 (d, J=13.5 Hz, 1H), 8.39 (d, J=13.7 Hz, 1H), 7.59-7.48 (m, 2H), 7.15-7.02 (m, 2H), 4.41 (q, 1=7.1 Hz, 2H), 3.19 (s, 3H), 1.43 (t, J=7.1 Hz, 3H).
Workup
- temperatureThe reaction was cooled
- temperaturethe reaction mixture was heated at 150° C. for 2 h
- temperatureThe reaction mixture was cooled
- concentrationconcentrated
- customthe residue was purified by column chromatography
- customto afford the desire product (1.08 g, 27% over 2 steps) as a tan solid
Sources & evidence
- ORD record
- ord-7a6ba4fde6524a91bdf9ae2827106e7b
- Source dataset
- uspto-grants-2015_09
- Patent number
- US09120749B2
Reaction notes
Loading…