Hydrochloric Acid → 2-Chloro-5-nitrophenol

HRID 880470Notes

Reaction equation

HRID 880470 reaction equation
N([O-])=O.[Na+].N[C:6]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][C:7]=1[OH:15].C(OCC)(=O)C.[ClH:22]>O.[Cu]Cl>[Cl:22][C:6]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][C:7]=1[OH:15]

Participants

7

Reactant 4

HCID 313Hydrochloric Acid2×HCID 8857Ethyl AcetateHCID 49847212-Amino-5-NitrophenolHCID 23668193Sodium Nitrite

Product 1

HCID 692642-Chloro-5-nitrophenolYield 92%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

A saturated solution of sodium nitrite (1.8 g, 26.0 mmol) in water (12 mL) was added dropwise to a suspension of 2-amino-5-nitro-phenol (2.0 g, 13.0 mmol) in concentrated hydrochloric acid (10 mL) at 0° C. and stirred for 30 min. A solution of Copper (I) chloride (5.15 g, 52.0 mmol) and concentrated hydrochloric acid (20 mL) heated to between 60 and 70° C. was added dropwise over a period of 30 min. The resultant reaction mixture was heated to 80° C. and stirred for 15 min and then allowed to cool to ambient temperature. Ethyl acetate (50 mL) was added and after stirring for 5 min the organic phase was separated and the aqueous phase was re-extracted with ethyl acetate (2×50 mL). The combined organic phases were washed with water (4×50 mL), brine, dried over anhydrous sodium sulfate and concentrated in vacuo to give a residue which was purified by column chromatography over silica gel (100-200 mesh) using 5% ethyl acetate in petroleum ether as eluent to afford 2-chloro-5-nitro-phenol (2.08 g, 92%) as a crystalline yellow solid.

Workup

  1. additionwas added dropwise over a period of 30 min
  2. customThe resultant reaction mixture
  3. stirringstirred for 15 min
  4. temperatureto cool to ambient temperature
  5. stirringafter stirring for 5 min the organic phase
  6. customwas separated
  7. extractionthe aqueous phase was re-extracted with ethyl acetate (2×50 mL)
  8. washThe combined organic phases were washed with water (4×50 mL), brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. concentrationconcentrated in vacuo
  11. customto give a residue which
  12. customwas purified by column chromatography over silica gel (100-200 mesh)

Sources & evidence

ORD record
ord-9598bea862054ab186a1a619f8c6489a
Source dataset
uspto-grants-2015_03
Patent number
US08993574B2

Reaction notes

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