Hydrogen Peroxide → 4-Bromo-2-iodoaniline

Temperature

50 °C

To a solution of 4-bromo-aniline (500 g, 2.90 mol, 2.0 equiv, Saibain Chem) in cyclohexane (2.5 L) was added iodine (368 g, 1.45 mol, 1.0 equiv, Qualigens) and the mixture was heated at 50° C. After 30 min, the reaction mixture became homogenous. 30% aqueous hydrogen peroxide solution (250 mL, Spectrochem) was added to the reaction mixture. The reaction was heated for 4 h at 50° C. The reaction was cooled to room temperature, diluted with ethyl acetate (5.0 L) and washed with aqueous sodium-sulphite (2.5 Kg in 4.0 L) solution. The organic layer was washed with water (3.0 L) and brine (3.0 L) dried over magnesium sulfate, filtered and concentrated under reduced pressure to obtain the crude material which was purified by column chromatography (silica gel; mesh size 60-120, elution 0-20% ethyl acetate and hexanes) to get 4-bromo-2-iodoaniline (650 g, 75.0%), as off white solid. TLC solvent system: 100% hexanes. Product's Rf: 0.6. MS (ESI, positive ion) m/z: 297.0 (M+1). 1H NMR (400 MHz, CDCl3) δ 7.72 (d, J=2.5 Hz, 1H), 7.23 (dd, J=8.4, 2.1 Hz, 1H), 6.62 (d, J=8.3 Hz, 1H), 4.09 (s, 2H).

1. temperatureThe reaction was heated for 4 h at 50° C
2. temperatureThe reaction was cooled to room temperature
3. washwashed with aqueous sodium-sulphite (2.5 Kg in 4.0 L) solution
4. washThe organic layer was washed with water (3.0 L) and brine (3.0 L)
5. dry with materialdried over magnesium sulfate
6. filtrationfiltered
7. concentrationconcentrated under reduced pressure
8. customto obtain the crude material which
9. customwas purified by column chromatography (silica gel; mesh size 60-120, elution 0-20% ethyl acetate and hexanes)

ORD record

ord-3c1af5740b344283a12d5bd1b1703bcf

Source dataset

uspto-grants-2015_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09212182B2