Sulfuric Acid → 4-Bromo-1-iodo-2-methoxybenzene

HRID 1432038Notes

Reaction equation

HRID 1432038 reaction equation
[Br:1][C:2]1[CH:8]=[CH:7][C:5](N)=[C:4]([O:9][CH3:10])[CH:3]=1.S(=O)(=O)(O)O.N([O-])=O.[Na+].[I-:20].[K+]>O.C(OCC)(=O)C>[Br:1][C:2]1[CH:8]=[CH:7][C:5]([I:20])=[C:4]([O:9][CH3:10])[CH:3]=1

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 4875Potassium IodideHCID 4592574-Bromo-2-methoxyanilineHCID 23668193Sodium Nitrite

Product 1

HCID 468357314-Bromo-1-iodo-2-methoxybenzene

Reagents, catalysts & solvents 2

HCID 962WaterSolvent3×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

4-Bromo-2-methoxy-aniline (20 g, 99 mmol) was dissolved in water (695 mL) and concentrated sulphuric acid (113 mL). The solution was cooled to 0° C. and sodium nitrite (7.5 g, 109 mmol) dissolved in water (32 mL) was added and stirred for 1 hour at 5-10° C. Potassium iodide (21.4 g, 129 mmol) dissolved in water (100 mL) was added slowly whilst the mixture was vigorously stirred. After addition, the mixture was allowed to warm to room temperature. Ethyl acetate was added and the phases were separated. The aqueous phase was extracted with ethyl acetetate (3×). The combined organic phases were then washed with 1M NaOH, 1M Na2S2O3, 1M HCl, 1M saturated NaHCO3 and brine. The separated organic phase was dried (MgSO4), filtered and concentrated in vacuo. The product was purified by flash chromatography using silica gel and eluting with heptane/ethyl acetate 1:1. The product was identified from relevant fractions which were combined and concentrated in vacuo.

Workup

  1. additionwas added
  2. additionwas added slowly whilst the mixture
  3. stirringwas vigorously stirred
  4. additionAfter addition
  5. temperatureto warm to room temperature
  6. customthe phases were separated
  7. extractionThe aqueous phase was extracted with ethyl acetetate (3×)
  8. washThe combined organic phases were then washed with 1M NaOH, 1M Na2S2O3, 1M HCl, 1M saturated NaHCO3 and brine
  9. dry with materialThe separated organic phase was dried (MgSO4)
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customThe product was purified by flash chromatography
  13. washeluting with heptane/ethyl acetate 1:1
  14. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-b9af0083a754420994ef68bf21fcfca8
Source dataset
uspto-grants-2009_11
Patent number
US07612068B2

Reaction notes

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