3,5-dichloro-4-methylaniline

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Suspend the 3,5-dichloro-4-methylaniline in 48% HBr (5 mL) and water (5 mL) and heat with a heat gun until the mixture is near the boiling point. Cool the slurry to room temperature and then cool to 0° C. with an ice/brine bath. Add a solution of sodium nitrite (109 mg, 1.58 mmol) in water (2 mL) dropwise. After the addition is complete, stir the reaction an additional 15 min in the cold bath. Add a solution of CuBr (1.08 g, 7.53 mmol) in 48% HBr (2 mL) and heat the rapidly stirring reaction to 50° C. for 1 hour. Cool the reaction to room temperature, dilute the reaction with ethyl acetate and discard the aqueous layer. Wash the organic layer with water and brine, dry with MgSO4, filter through celite and concentrate to an orange residue. Purify the residue by silica gel chromatography eluting with hexanes to afford 164 mg (45%) of the product as a yellow solid. heat with a heat gun until the mixture cool to 0° C. with an ice/brine bath After the addition the reaction an additional 15 min in the cold bath heat the rapidly stirring reaction to 50° C. for 1 hour Cool the reaction to room temperature dilute Wash the organic layer with water and brine dry with MgSO4 filter through celite concentrate to an orange residue Purify the residue by silica gel chromatography eluting with hexanes

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Dissolve 1,3-dichloro-2-methyl-5-nitrobenzene (0.50 g, 2.43 mmol) in DMF and treat with tin (II) chloride dihydrate (2.74 g, 12.1 mmol) in a single portion. Stir the reaction for 1 hour and dilute with ethyl acetate and filter through celite. Wash the filtrate four times with water and twice with brine, dry over MgSO4, filter and concentrate to a dark oil. Purify the residue by silica gel chromatography eluting with a gradient of 5% to 10% ethyl acetate in hexanes to give 342 mg (80%) of the titled product as white flakes. the reaction for 1 hour filter through celite Wash the filtrate four times with water twice with brine, dry over MgSO4 filter concentrate to a dark oil Purify the residue by silica gel chromatography eluting with a gradient of 5% to 10% ethyl acetate in hexanes

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Dissolve 1,3-dichloro-2-methyl-5-nitrobenzene (0.50 g, 2.43 mmol) in DMF and treat with tin (II) chloride dihydrate (2.74 g, 12.1 mmol) in a single portion. Stir the reaction for 1 hour and dilute with ethyl acetate and filter through celite. Wash the filtrate four times with water and twice with brine, dry over MgSO4, filter and concentrate to a dark oil. Purify the residue by silica gel chromatography eluting with a gradient of 5% to 10% ethyl acetate in hexanes to give 342 mg (80%) of the titled product as white flakes. the reaction for 1 hour filter through celite Wash the filtrate four times with water twice with brine, dry over MgSO4 filter concentrate to a dark oil Purify the residue by silica gel chromatography eluting with a gradient of 5% to 10% ethyl acetate in hexanes

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Dissolve 1,3-dichloro-2-methyl-5-nitrobenzene (0.50 g, 2.43 mmol) in DMF and treat with tin (II) chloride dihydrate (2.74 g, 12.1 mmol) in a single portion. Stir the reaction for 1 hour and dilute with ethyl acetate and filter through celite. Wash the filtrate four times with water and twice with brine, dry over MgSO4, filter and concentrate to a dark oil. Purify the residue by silica gel chromatography eluting with a gradient of 5% to 10% ethyl acetate in hexanes to give 342 mg (80%) of the titled product as white flakes. the reaction for 1 hour filter through celite Wash the filtrate four times with water twice with brine, dry over MgSO4 filter concentrate to a dark oil Purify the residue by silica gel chromatography eluting with a gradient of 5% to 10% ethyl acetate in hexanes

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Suspend 3,5-dichloro-4-methylaniline in 48% HBr (5 mL) and water (5 mL) and heat with a heat gun until the mixture is near the boiling point. Cool the slurry to room temperature and then cool to 0° C. with an ice/brine bath. Add dropwise a solution of sodium nitrite (109 mg, 1.58 mmol) in water (2 mL). After the addition is complete, stir the reaction an additional 15 min in the cold bath. Add a solution of CuBr (1.08 g, 7.53 mmol) in 48% HBr (2 mL) and heat the rapidly stirring reaction to 50° C. for 1 hour. Cool the reaction to room temperature, dilute with EtOAc and discard the aqueous layer. Wash the organic layer with water and brine, dry with MgSO4, filter through celite and concentrate to an orange residue. Purify the residue by silica gel chromatography eluting with hexanes to afford 164 mg (45%) of the product as a yellow solid. heat with a heat gun until the mixture cool to 0° C. with an ice/brine bath After the addition the reaction an additional 15 min in the cold bath heat the rapidly stirring reaction to 50° C. for 1 hour Cool the reaction to room temperature Wash the organic layer with water and brine dry with MgSO4 filter through celite concentrate to an orange residue Purify the residue by silica gel chromatography eluting with hexanes

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Dissolve 1,3-dichloro-2-methyl-5-nitrobenzene (0.50 g, 2.43 mmol) in DMF and treat with tin (II) chloride dihydrate (2.74 g, 12.1 mmol) in a single portion. Stir the reaction for 1 hour, dilute with ethyl acetate, and filter through celite. Wash the filtrate four times with water and twice with brine, dry over MgSO4, filter and concentrate to a dark oil. Purify the residue by silica gel chromatography eluting with a gradient of 5% to 10% ethyl acetate in hexanes to give 342 mg (80%) of the titled product as white flakes. the reaction for 1 hour filter through celite Wash the filtrate four times with water twice with brine, dry over MgSO4 filter concentrate to a dark oil Purify the residue by silica gel chromatography eluting with a gradient of 5% to 10% ethyl acetate in hexanes

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 61.5 parts of 2,3,5,6-tetrachloro-4-methylaniline, 180 parts of phenol and 15 parts of a 1% strength palladium/charcoal catalyst are reacted with hydrogen under a maximum pressure of 50 bar at 180° C. in a tantalum autoclave, in the presence of a small amount of hydrochloric acid, in the course of 5 hours, while stirring. After the pressurized vessel has been cooled and the pressure released, the mixture is diluted with 300 parts of water and 200 parts of toluene, rendered alkaline, heated to 90°, and separated from the catalyst. The catalyst is boiled up with toluene, and the combined toluene solutions are distilled. 44 parts of 3,5-dichloro-4-methylaniline, bp. 146°-155°/18 mbar, 98% strength, are obtained; yield: 98% of theory. After the pressurized vessel has been cooled heated to 90° separated from the catalyst the combined toluene solutions are distilled

反応条件: temp:0.00; pressure:0.00; stir: