(2,4-dichloro-5-propan-2-yloxyphenyl)hydrazine

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 15.8 g (0.23 mole) of sodium nitrite in 100 mL of water was added to a stirred solution of 50.0 g (0.23 mole) of 2,4-dichloro-5-(1-methylethoxy)aniline in 250 mL of concentrated hydrochloric acid at 0° C. over 30 minutes. After complete addition, the mixture was stirred at 0° C. for 30 minutes. A solution of 114.0 g (0.506 mole) of tin (II) chloride dihydrate in 125 mL of concentrated hydrochloric acid was added dropwise to the reaction mixture. After complete addition, the mixture was stirred for one hour. The resultant white slurry was filtered. The filter cake was added to a 20% aqueous sodium hydroxide solution and stirred for 30 minutes. The basic mixture was filtered, and the filter cake recrystallized from methanol and water to yield 37.0 g of 2,4-dichloro-5-(1-methylethoxy)phenylhydrazine. After complete addition After complete addition the mixture was stirred for one hour The resultant white slurry was filtered The filter cake was added to a 20% aqueous sodium hydroxide solution stirred for 30 minutes The basic mixture was filtered the filter cake recrystallized from methanol and water

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 15.8 g (0.23 mole) of sodium nitrite in 100 mL of water was added to a stirred solution of 50.0 g (0.23 mole) of 2,4-dichloro-5-(1-methylethoxy)aniline in 250 mL of concentrated hydrochloric acid at 0° C. over 30 minutes. After complete addition, the mixture was stirred at 0° C. for 30 minutes. A solution of 114.0 g (0.506 mole) of tin (II) chloride dihydrate in 125 mL of concentrated hydrochloric acid was added dropwise to the reaction mixture. After complete addition, the mixture was stirred for one hour. The resultant white slurry was filtered. The filter cake was added to a 20% aqueous sodium hydroxide solution and stirred for 30 minutes. The basic mixture was filtered, and the filter cake recrystallized from methanol and water to yield 37.0 g of 2,4-dichloro-5-(1-methylethoxy)phenylhydrazine. After complete addition After complete addition the mixture was stirred for one hour The resultant white slurry was filtered The filter cake was added to a 20% aqueous sodium hydroxide solution stirred for 30 minutes The basic mixture was filtered the filter cake recrystallized from methanol and water

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 15.8 g (0.23 mole) of sodium nitrite in 100 mL of water was added to a stirred solution of 50.0 g (0.23 mole) of 2,4-dichloro-5-(1-methylethoxy)aniline in 250 mL of concentrated hydrochloric acid at 0° C. over 30 minutes. After complete addition, the mixture was stirred at 0° C. for 30 minutes. A solution of 114.0 g (0.506 mole) of tin (II) chloride dihydrate in 125 mL of concentrated hydrochloric acid was added dropwise to the reaction mixture. After complete addition, the mixture was stirred for one hour. The resultant white slurry was filtered. The filter cake was added to a 20% aqueous sodium hydroxide solution and stirred for 30 minutes. The basic mixture was filtered, and the filter cake recrystallized from methanol and water to yield 37.0 g of 2,4-dichloro-5-(1-methylethoxy)phenylhydrazine. After complete addition After complete addition the mixture was stirred for one hour The resultant white slurry was filtered The filter cake was added to a 20% aqueous sodium hydroxide solution stirred for 30 minutes The basic mixture was filtered the filter cake recrystallized from methanol and water

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

実験手順: Under a dry nitrogen atmosphere a stirred solution of 2.4 g (0.01 mole) of 2,4-dichloro-5-(1-methylethoxy)phenylhydrazine in 140 mL of methanol was cooled to -60° C. in a dry ice-isopropanol bath. Trifluoroacetonitrile (23.2 g, 0.24 mole) was bubbled into the cold solution during a two minute period. After complete addition the cold solution was stirred for 30 minutes, then allowed to warm slowly to room temperature during the next three hours. A stream of nitrogen gas was bubbled into the room temperature solution to aid in the vaporization and removal of trifluoroacetonitrile, leaving a liquid residue. This residue was evaporated further under reduced pressure to leave a resinous material. This material was stirred in cold pentane to produce a solid. The pentane was decanted and the solid triturated in fresh cold pentane. The pentane was decanted and the solid dried under reduced pressure to yield 2.9 g of N-[2,4-dichloro-5-(1-methylethoxy)anilino]trifluoroacetamidine (mp 80.5°-81° C.). After complete addition the cold solution A stream of nitrogen gas was bubbled into the room temperature solution to aid in the vaporization and removal of trifluoroacetonitrile leaving a liquid residue This residue was evaporated further under reduced pressure to leave a resinous material to produce a solid The pentane was decanted the solid triturated in fresh cold pentane The pentane was decanted the solid dried under reduced pressure

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

実験手順: To a stirred solution of 11.8 g (0.05 mole) of 2,4-dichloro-5-(1-methylethoxy)phenylhydrazine and 10.0 g (0.06 mole) of ethyl difluoroacetylcarbamate in 130 mL of xylene was added 2.5 g (0.02 mole) of phosphorus pentoxide. After complete addition the mixture was heated at reflux for 1.5 hours then allowed to cool to room temperature for approximately 18 hours. The reaction mixture was decanted from a dark residue in the reaction flask and washed with water. The washed mixture was extracted with a 10% aqueous sodium hydroxide solution. The basic extract was made acidic with concentrated hydrochloric acid to form an oily precipitate. This aqueous phase was decanted from the oily residue and fresh water added to wash the residue. This residue was dissolved in 160 mL of methylene chloride and filtered through a celite pad. The filtrate was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to leave a semi-solid residue. The residue was triturated with approximately 125 mL of petroleum ether to provide 8.2 g of 1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one. After complete addition the mixture was heated at reflux for 1.5 hours The reaction mixture was decanted from a dark residue in the reaction flask washed with water The washed mixture was extracted with a 10% aqueous sodium hydroxide solution The basic extract to form an oily precipitate This aqueous phase was decanted from the oily residue and fresh water added to wash the residue This residue was dissolved in 160 mL of methylene chloride filtered through a celite pad The filtrate was dried over anhydrous magnesium sulfate filtered The filtrate was evaporated under reduced pressure to leave a semi-solid residue The residue was triturated with approximately 125 mL of petroleum ether

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 15.8 g (0.23 mole) of sodium nitrite in 100 mL of water was added to a stirred solution of 50.0 g (0.23 mole) of 2,4-dichloro-5-(1-methylethoxy)aniline in 250 mL of concentrted hydrochloric acid at 0° C. over 30 minutes. After complete addition, the mixture was stirred at 0° C. for 30 minutes. A solution of 114.0 g (0.506 mole) of tin (II) chloride dihydrate in 125 mL of concentrated hydrochloric acid was added dropwise to the reaction mixture. After complete addition, the mixture was stirred for one hour. The resultant white slurry was filtered. The filter cake was added to a 20% aqueous sodium hydroxide solution and stirred for 30 minutes. The basic mixture was filtered, and the filter cake recrystallized from methanol and water to yield 37.0 g of 2,4-dichloro-5-(1-methylethoxy)phenylhydrazine. After complete addition After complete addition the mixture was stirred for one hour The resultant white slurry was filtered The filter cake was added to a 20% aqueous sodium hydroxide solution stirred for 30 minutes The basic mixture was filtered the filter cake recrystallized from methanol and water