4'-Chloro-3'-nitroacetophenone → 2-Bromo-1-(4-chloro-3-nitrophenyl)ethan-1-one

To a flask equipped with a magnetic stir bar and under an atmosphere of N2 was added 4′-chloro-3′-nitroacetophenone (10.0 g, 50.1 mmol) and THF (100 mL). To this stirring mixture was added portion-wise phenyltrimethylammonium tribromide (19.78 g, 52.6 mmol) over a 15 minutes time period. The resultant mixture was then stirred with monitoring every hour via LCMS. After 3 hr the mixture was then filtered and resulting solids washed with EtOAc. The organic solution was then concentrated, H2O and 10% aq. NaHCO3 added and washed with EtOAc (2×300 mL). The combined organic layers were then washed with Brine, dried (MgSO4), filtered and concentrated. The residue material was then subjected to purification via crystallization (dissolved material in 100 mL EtOAc and slowly added hexanes until cloudy—let stand for a few hours) to yield 9.81 g (70%) of 2-bromo-1-(4-chloro-3-nitrophenyl)ethanone as an off white colored solid product. 1H NMR (500 MHz, DMSO-D6) δ ppm 5.00 (s, 2H) 7.98 (d, J=8.54 Hz, 1H) 8.24 (dd, J=8.54, 2.14 Hz, 1H) 8.61 (d, J=1.98 Hz, 1H).

1. customTo a flask equipped with a magnetic stir bar and under an atmosphere of N2
2. waitwith monitoring every hour via LCMS
3. filtrationAfter 3 hr the mixture was then filtered
4. customresulting solids
5. washwashed with EtOAc
6. concentrationThe organic solution was then concentrated
7. additionH2O and 10% aq. NaHCO3 added
8. washwashed with EtOAc (2×300 mL)
9. washThe combined organic layers were then washed with Brine
10. dry with materialdried (MgSO4)
11. filtrationfiltered
12. concentrationconcentrated
13. customThe residue material was then subjected to purification via crystallization (
14. dissolutiondissolved material in 100 mL EtOAc

ORD record

ord-d86950ecd26b428fbdcc714b6c1eb8e7

Source dataset

uspto-grants-2015_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09006387B2