3-chloro-4-methylphenol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 245.0 g of 3A was mixed with 1.6 liters of glacial acetic acid, and the resulting solution was stirred at 8°-10° C. while 109.6 g of 90% aqueous nitric acid was added (two hours). The mixture was stirred at 10°-15° C. for five hours, poured over ice water and extracted with ether/hexane. The extract was washed with water, dried and stripped to dryness. The residue was stirred with 3 liters of hexane and the hexane solution was filtered through silica gel. The filtrate was held at -20° C. for 16 hours, filtered, and the filtrate was concentrated to one liter, charcoaled, then held at -30° to -35° C. for two hours and filtered. The solid products were combined to give 3-chloro-4-methyl-6-nitrophenol (3B). was added (two hours) extracted with ether/hexane The extract was washed with water dried The residue was stirred with 3 liters of hexane the hexane solution was filtered through silica gel The filtrate was held at -20° C. for 16 hours filtered the filtrate was concentrated to one liter held at -30° to -35° C. for two hours filtered

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 245.0 g of 3A was mixed with 1.6 liters of glacial acetic acid, and the resulting solution was stirred at 8°-10° C. while 109.6 g of 90% aqueous nitric acid was added (two hours). The mixture was stirred at 10°-15° C. for five hours, poured over ice water and extracted with ether/hexane. The extract was washed with water, dried and stripped to dryness. The residue was stirred with 3 liters of hexane and the hexane solution was filtered through silica gel. The filtrate was held at -20° C. for 16 hours, filtered, and the filtrate was concentrated to one liter, charcoaled, then held at -30° to -35° C. for two hours and filtered. The solid products were combined to give 3-chloro-4-methyl-6-nitrophenol (3B). was added (two hours) extracted with ether/hexane The extract was washed with water dried The residue was stirred with 3 liters of hexane the hexane solution was filtered through silica gel The filtrate was held at -20° C. for 16 hours filtered the filtrate was concentrated to one liter held at -30° to -35° C. for two hours filtered

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 283.0 g of 3-chloro-4-methylaniline, 1000 ml of water and 500 ml of concentrated sulfuric acid were mixed, initially at room temperature. The temperature of the mixture rose to 95° C. The mixture was stirred at room temperature for 30 minutes, cooled to 5° C. and a solution of 145 g of sodium nitrite in 500 ml of water was slowly added (1.5 hours) to the stirred mixture at 5°-10° C., then the mixture was stirred at about 5° C. for one hour. The resulting solution was added over two hours to a stirred solution of 1.2 liters of concentrated sulfuric acid in 2 liters of water, at 105°-110° C., and the resulting mixture was stirred at 110° C. for one hour, then held at room temperature for 18 hours. Then 3.5 liters of hexane was added, the mixture was stirred for 30 minutes, allowed to stand, and the two liquid phases were separated. The hexane phase was filtered, washed with water, dried (MgSO4) and concentrated to dryness to give crude (91%) 3-chloro-4-methylphenol (3A). rose to 95° C cooled to 5° C. the mixture was stirred at about 5° C. for one hour the resulting mixture was stirred at 110° C. for one hour held at room temperature for 18 hours the mixture was stirred for 30 minutes the two liquid phases were separated The hexane phase was filtered washed with water dried (MgSO4) concentrated to dryness