Sulfuric Acid → 3-Chloro-4-methylphenol

HRID 637633Notes

Reaction equation

HRID 637633 reaction equation
S(=O)(=O)(O)O.[Cl:6][C:7]1[CH:8]=[C:9]([CH:11]=[CH:12][C:13]=1[CH3:14])N.N([O-])=[O:16].[Na+]>O>[Cl:6][C:7]1[CH:8]=[C:9]([OH:16])[CH:11]=[CH:12][C:13]=1[CH3:14]

Participants

5

Reactant 3

HCID 1118Sulfuric Acid2×HCID 72553-Chloro-4-methylanilineHCID 23668193Sodium Nitrite

Product 1

HCID 148533-Chloro-4-methylphenol

Reagents, catalysts & solvents 1

HCID 962WaterSolvent3×

Conditions

Temperature
104 °C

Procedure

1.3 liters of concentrated sulfuric acid was added to a stirred mixture of 566 g of 3-chloro-4-methylaniline and 3 liters of water. The mixture warmed to 104° C. The mixture was cooled to 10°-15° C. and stirred while a solution of 290 g sodium nitrite in 1 liter of water was added drop-by-drop (over 2 hours). The mixture was stirred for 1 hour at about 10° C., then was added drop-by-drop (over 2 hours) to a stirred solution of 1 liter of concentrated sulfuric acid in 1.5 liters of water, at 110°-115° C. The resulting mixture was stirred at reflux temperature for one hour, cooled to room temperature and extracted with ether. The extract (4 liters) was mixed with 4 liters of water. The resulting mixture was stirred at 15° C. while 700 ml of a 50% aqueous solution of sodium hydroxide was slowly added (over 1 hour). The aqueous phase was separated, cooled to 15°-20° C. and stirred while 1.3 liters of concentrated hydrochloric acid was added. The resulting mixture was extracted with ether, the extract was dried (MgSO4) and the solvent was evaporated to give 3-chloro-4-methylphenol (4A), as an amber oil.

Workup

  1. temperatureThe mixture was cooled to 10°-15° C.
  2. additionwas added drop-by-drop (over 2 hours)
  3. stirringThe resulting mixture was stirred
  4. temperatureat reflux temperature for one hour
  5. temperaturecooled to room temperature
  6. extractionextracted with ether
  7. extractionThe extract (4 liters)
  8. additionwas mixed with 4 liters of water
  9. stirringThe resulting mixture was stirred at 15° C. while 700 ml of a 50% aqueous solution of sodium hydroxide
  10. additionwas slowly added (over 1 hour)
  11. customThe aqueous phase was separated
  12. temperaturecooled to 15°-20° C.
  13. stirringstirred while 1.3 liters of concentrated hydrochloric acid
  14. additionwas added
  15. extractionThe resulting mixture was extracted with ether
  16. dry with materialthe extract was dried (MgSO4)
  17. customthe solvent was evaporated

Sources & evidence

ORD record
ord-3c4e7a0b15024d80a2a66d81705118f9
Source dataset
uspto-grants-1985_12
Patent number
US04558040

Reaction notes

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