Sulfuric Acid → 3-Chloro-4-methylphenol

Participants

Reaction Conditions

Reaction Steps

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.

Provenance & Evidence