Sodium Sulfite → 4-Iodo-3-nitro-2-chloroaniline

HRID 2120372Notes

Reaction equation

HRID 2120372 reaction equation
[I:1]Cl.[N+:3]([C:6]1[C:7]([Cl:13])=[C:8]([CH:10]=[CH:11][CH:12]=1)[NH2:9])([O-:5])=[O:4].S([O-])([O-])=O.[Na+].[Na+]>C(O)(=O)C>[I:1][C:12]1[CH:11]=[CH:10][C:8]([NH2:9])=[C:7]([Cl:13])[C:6]=1[N+:3]([O-:5])=[O:4]

Participants

5

Reactant 3

HCID 24437Sodium SulfiteHCID 24640Iodine chlorideHCID 142200162-Chloro-3-nitroaniline

Product 1

HCID 234394594-Iodo-3-nitro-2-chloroaniline

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
70 °C

Procedure

Iodine monochloride (1.25 ml) was added to a solution of 3-nitro-2-chloroaniline (4265 mg) in glacial acetic acid (40 ml). The mixture was stirred for four hours at 70° C. After the mixture was allowed to cool to ambient temperature, saturated sodium sulphite solution (100 ml) was added. The solution was extracted with EtOAc (200 ml), volatile material was removed by evaporation and the residue was redissolved in EtOAc (150 ml), washed with saturated sodium bicarbonate solution (75 ml), brine (75 ml) and dried. The volatile material was removed by evaporation and the residue was purified by chromatography eluting with 5-15% EtOAc in hexane to give a mixture of the title compound and the starting material (1.933 g) (ratio 1:1.75). Iodine monochloride (0.28 ml) was added to a solution of the mixture (1919 mg) in glacial acetic acid (10 ml). The mixture was stirred for four hours at 70° C. After the mixture was allowed to cool to ambient temperature, saturated sodium sulphite solution (50 ml) added. The solution was extracted with EtOAc (100 ml), volatile material was removed by evaporation and the residue was partitioned between EtOAc (100 ml) and saturated sodium bicarbonate solution (50 ml). The organic phase was separated, washed with brine (50 ml) and dried. The volatile material was removed by evaporation and the residue was purified by chromatography eluting with 5-15% EtOAc in hexane to give the title compound (1286 mg) as a solid. NMR: 6.19 (s, 2H), 6.73 (d, 1H), 7.50 (d, 1H); m/z 297.

Workup

  1. temperatureto cool to ambient temperature
  2. extractionThe solution was extracted with EtOAc (200 ml), volatile material
  3. customwas removed by evaporation
  4. dissolutionthe residue was redissolved in EtOAc (150 ml)
  5. washwashed with saturated sodium bicarbonate solution (75 ml), brine (75 ml)
  6. customdried
  7. customThe volatile material was removed by evaporation
  8. customthe residue was purified by chromatography
  9. washeluting with 5-15% EtOAc in hexane
  10. customto give

Sources & evidence

ORD record
ord-9c026cc2e5234c5aa2444a17eb3f962b
Source dataset
uspto-grants-2004_02
Patent number
US06689909B1

Reaction notes

Loading…