4-(Methylthio)aniline → 2-Bromo-4-(methylthio)aniline

To a solution containing 1.0 mL (8.0 mmol) of 4-(methylthio)aniline in 40 mL of a 3:1 solution mixture of acetonitrile/carbon tetrachloride was added 1.6 g (8.8 mmol) of N-bromosuccinimide. The reaction mixture was heated to reflux for 30 min, then cooled to ambient temperature and concentrated in vacuo. To the residue was added 100 mL of ethyl acetate and the organic solution was washed sequentially with saturated aqueous sodium bicarbonate solution and saturated aqueous brine (100 mL each), dried over sodium sulfate, filtered and evaporated in vacuo to yield a viscous oil. The crude material was purified by flash chromatography on a Biotage Horizon® system (silica gel, 0 to 30% ethyl acetate/hexanes gradient) to give the title compound. 1H NMR (CDCl3): δ 7.45 (s, 1H), 7.15 (dd, J=8.3, 2.0 Hz, 1H), 6.72 (d, 8.5 Hz, 1H), 4.08 (bs, NH2), 2.44 (s, 3H).

1. temperatureThe reaction mixture was heated
2. temperatureto reflux for 30 min
3. concentrationconcentrated in vacuo
4. additionTo the residue was added 100 mL of ethyl acetate
5. washthe organic solution was washed sequentially with saturated aqueous sodium bicarbonate solution and saturated aqueous brine (100 mL each)
6. dry with materialdried over sodium sulfate
7. filtrationfiltered
8. customevaporated in vacuo
9. customto yield a viscous oil
10. customThe crude material was purified by flash chromatography on a Biotage Horizon® system (silica gel, 0 to 30% ethyl acetate/hexanes gradient)

ORD record

ord-abe4eb29cadb43638acae513ca4d4f93

Source dataset

uspto-grants-2010_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07718667B2