2-Methoxyaniline → 4-Bromo-2-methoxyaniline

A solution of o-Anisidine (5.46 g, 44.3 mmol) in dichloromethane (100 mL) was treated with 2,4,4,6-tetrabromo-2,5-cyclohexadiene-1-one (18.16 g, 44.3 mmol) portion-wise over 1 h at −5° C. Following the addition of the brominating agent, the dry ice/acetone bath was removed and the reaction mixture stirred over night at room temperature. Sodium hydroxide solution (1N) was added to the reaction mixture, and the layers were partitioned. The organic layer was washed with 1 N sodium hydroxide solution (1 L), washed with water (750 mL), dried over magnesium sulfate, filtered, and evaporated under reduced pressure, to give 8.096 g (89%) of 4-bromo-2-methoxyaniline. 1H NMR (DMSO-d6, 400 MHz) δ 6.90 (s, 1H), 6.83-6.76 (m, 1H), 6.57-6.55 (m, 1H), 4.86 (s, 2H), 3.76 (s, 3H); HPLC Waters 2690 Alliance HPLC (Symmetry Shield RP18 3.5 μm, 2.1×50 mm; 5%-95% acetonitrile-0.1 M ammonium acetate over 15 min, 0.5 mL/min) Rt 5.635 min (89%).

1. additionthe addition of the brominating agent
2. customthe dry ice/acetone bath was removed
3. additionSodium hydroxide solution (1N) was added to the reaction mixture
4. customthe layers were partitioned
5. washThe organic layer was washed with 1 N sodium hydroxide solution (1 L)
6. washwashed with water (750 mL)
7. dry with materialdried over magnesium sulfate
8. filtrationfiltered
9. customevaporated under reduced pressure

ORD record

ord-f25e72241dd74dc5a0ee3547c2767f29

Source dataset

uspto-grants-2005_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06921763B2