(Diethylamino)sulfur trifluoride → 1-Bromo-4-chloro-2-(fluoromethyl)benzene

To a suspension of 2-bromo-5-chlorobenzyl alcohol (2.0 g, 9.0 mmol, Fluorochem) in anhydrous DCM (30 mL) was added (diethylamino)sulfur trifluoride (1.30 mL, 10 mmol), at about −75° C. After complete addition the mixture was allowed to warm slowly to rt, over about 1 h. Then saturated aqueous sodium bicarbonate (8 mL) was added and the mixture was partitioned between DCM (20 mL) and water (20 mL). The layers were separated and the aqueous layer was extracted twice with DCM (20 mL). The combined organic layers were washed with brine (20 mL), dried (MgSO4), filtered and concentrated in vacuo. The residue was purified by column chromatography (SiO2, DCM/hexanes 1:1) to give 1-bromo-4-chloro-2-(fluoromethyl)benzene (1.31 g, 5.9 mmol, 65%) as a pale yellow oil: 1H-NMR (CDCl3, Bruker 400 MHz) δ 5.42 (2 H, d, J=47.0 Hz) 7.19 (1 H, dd, J=8.8, 2.5 Hz) 7.41 (1 H, d, J=2.5 Hz) 7.48 (1 H, d, J=8.8 Hz).

1. customat about −75° C
2. additionAfter complete addition the mixture
3. customthe mixture was partitioned between DCM (20 mL) and water (20 mL)
4. customThe layers were separated
5. extractionthe aqueous layer was extracted twice with DCM (20 mL)
6. washThe combined organic layers were washed with brine (20 mL)
7. dry with materialdried (MgSO4)
8. filtrationfiltered
9. concentrationconcentrated in vacuo
10. customThe residue was purified by column chromatography (SiO2, DCM/hexanes 1:1)

ORD record

ord-2a78b3a1132b4efeb2bafac09f94336f

Source dataset

uspto-grants-2015_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09150592B2