Hydrochloric Acid → 2-Benzyloxy-5-nitroiodobenzene

HRID 565378Notes

Reaction equation

HRID 565378 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5](S([N-]Cl)(=O)=O)=[CH:4][CH:3]=1.O.O.O.[Na+].[N+:17]([C:20]1[CH:25]=[CH:24][C:23]([OH:26])=[CH:22][CH:21]=1)([O-:19])=[O:18].[I-:27].[Na+].Cl.C(Br)C1C=CC=CC=1.C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.O>[CH2:1]([O:26][C:23]1[CH:24]=[CH:25][C:20]([N+:17]([O-:19])=[O:18])=[CH:21][C:22]=1[I:27])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 9804-NitrophenolHCID 5238Sodium IodideHCID 7498Benzyl BromideHCID 11430Potassium CarbonateHCID 517414chloramine-T trihydrate

Product 1

HCID 226181932-Benzyloxy-5-nitroiodobenzeneYield 64%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6228DimethylformamideSolvent

Procedure

Chloramine-T trihydrate (36 g, 127 mmol) was added to a mixture of 4-nitrophenol (15 g, 107 mmol) and sodium iodide (19.1 g, 127 mmol) in DMF (300 ml) at room temperature. The resulting dark red mixture was stirred at room temperature for 3 hours, poured into water (1.2 litres), acidified to pH 1 with aqueous hydrochloric acid (1M) and extracted with ethyl acetate. The organic extract was washed with sodium thiosulphate solution (10%) and brine, dried (MgSO4) and the solvent was evaporated under reduced pressure. The residue was purified by flash column chromatography on silica gel eluting with hexane/ethyl acetate (50:50). The residue was dissolved in DMF (75 ml) and benzyl bromide (10.7 ml, 90 mmol) and potassium carbonate (66 g, 480 mmol) were added. The mixture was stirred at room temperature over night, poured into water (1 litre) and extracted with ethyl acetate. The organic extract was washed with brine, dried (MgSO4), and the solvent was evaporated under reduced pressure. The residue was purified by flash column chromatography on silica gel eluting with hexane/dichloromethane/ethyl acetate (50:50:1) to give the title compound as a colorless solid (24.3 g, 64%). 1H NMR (360 MHz, CDCl3) δ 8.70 (1H, d, J 2.7 Hz), 8.21 (1H, dd, J 9.13, 2.7 Hz), 7.48−7.34 (5H, m), 6.89 (1H, d, J 9.14 Hz), and 5.27 (2H, s).

Workup

  1. extractionextracted with ethyl acetate
  2. extractionThe organic extract
  3. washwas washed with sodium thiosulphate solution (10%) and brine
  4. dry with materialdried (MgSO4)
  5. customthe solvent was evaporated under reduced pressure
  6. customThe residue was purified by flash column chromatography on silica gel eluting with hexane/ethyl acetate (50:50)
  7. dissolutionThe residue was dissolved in DMF (75 ml)
  8. stirringThe mixture was stirred at room temperature over night
  9. extractionextracted with ethyl acetate
  10. extractionThe organic extract
  11. washwas washed with brine
  12. dry with materialdried (MgSO4)
  13. customthe solvent was evaporated under reduced pressure
  14. customThe residue was purified by flash column chromatography on silica gel eluting with hexane/dichloromethane/ethyl acetate (50:50:1)

Sources & evidence

ORD record
ord-91abc8e6e9af44abbf92ed6c8ca88d04
Source dataset
uspto-grants-2001_01
Patent number
US06172077B2

Reaction notes

Loading…