Hydrogen Peroxide → 3,4-Dichloro-2-iodoaniline

To a stirred suspension of 3,4-dichloroaniline (20 g, 123 mmol), HI (48%, 15.7 g, 123 mmol), H2O2 (30%, 8.3 g, 246 mmol) in H2O (62 mL) at r.t. The reaction mixture was stirred in dark at r.t for overnight. The supernatant was discarded, diluted with ethyl acetate:hexanes (1:10), quenched with saturates NaHSO3, stirred for 1 h at ambient temperature, filtered the solids. The filtrate was washed with water, saturated aqueous NaHCO3, dried (Na2SO4), filtered and concentrated to get 1:4 regioisomeric mixture of iodo derivative (minor isomer is required). It was recrystallized from cyclohexane to afford 1:1 mixture of regioisomers enriched in the filtrate. This mixture was further purified by flash column chromatography on silica gel, eluting with ethyl acetate:hexanes (0-2%) to get the required compound as a cream color solid (5.2 g, ˜15% yield). 1H NMR (400 MHz, CDCl3) δ 7.22 (d, J=8.6 Hz, 1H), 6.60 (d, J=8.6 Hz, 1H), 4.32 (br, 2H).

1. customquenched with saturates NaHSO3
2. stirringstirred for 1 h at ambient temperature
3. filtrationfiltered the solids
4. washThe filtrate was washed with water, saturated aqueous NaHCO3
5. dry with materialdried (Na2SO4)
6. filtrationfiltered
7. concentrationconcentrated
8. customto get
9. customIt was recrystallized from cyclohexane
10. customto afford
11. addition1:1 mixture of regioisomers
12. customThis mixture was further purified by flash column chromatography on silica gel
13. washeluting with ethyl acetate

ORD record

ord-6ed071891f564b8f83be254d0fc91d7b

Source dataset

uspto-grants-2016_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09340509B2