3-chloro-2-propan-2-ylsulfanylaniline

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:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 40 g of 2-chloro-6-nitrophenyl-isopropylsulfane, 160 g of methanol and 2.4 g of Raney nickel 37-1 (methanol-moist) were initially introduced into a 0.7 l steel autoclave. After rinsing with nitrogen, 70 bar of hydrogen were forced in and the contents of the autoclave were heated to 100° C., while stirring. The hydrogen pressure was increased to 80 bar. After 50 minutes, the uptake of hydrogen had ended. The mixture was kept under the reaction conditions for a further 30 minutes. After cooling, letting down the hydrogen and removing the catalyst, the solvent was distilled off. Crude 2-amino-6-chlorophenyl-isopropylsulfane was already obtained as a 99% pure product (GC) which contained only 0.2% of 2-aminophenyl-isopropylsulfane (formed by dechlorination) and only 0.3% of m-chloroaniline (formed by desulfurization). The yield was 34.5 g. After rinsing with nitrogen, 70 bar of hydrogen The hydrogen pressure was increased to 80 bar The mixture was kept under the reaction conditions for a further 30 minutes After cooling removing the catalyst the solvent was distilled off

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 46.6 g of 2-chloro-6-nitrophenyl-isopropylsulfane, 160 ml of methanol and 5 g of Raney nickel 55 (water-moist, washed with methanol) were introduced into a steel autoclave. After flushing with nitrogen and hydrogen, the mixture was heated to 50° C., while stirring, and hydrogenation was carried out by forcing in hydrogen up to a maximum of 2 bar. After 2.5 hours, the uptake of hydrogen had ended. The mixture was then cooled to room temperature, the hydrogen was let down and the nickel catalyst was removed by filtration with suction and washed with methanol. After removal of the solvent, 39.9 g of 2-amino-6-chlorophenyl-isopropylsulfane were obtained in a purity of 97.8% (GC), which corresponds to 97% of theory. Only 0.2% of 2-aminophenylisopropylsulfane (formed by dehalogenation) was found as an impurity. Pure, colorless 2-amino-6-chlorophenyl-isopropylsulfane with a content of more than 99% was obtained by distillation at a boiling point of 144° C. at 11 mbar. After flushing with nitrogen and hydrogen The mixture was then cooled to room temperature the nickel catalyst was removed by filtration with suction washed with methanol After removal of the solvent

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:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 40 g of 2-chloro-6-nitrophenyl-isopropylsulfane, 160 g of methanol and 2.4 g of Raney nickel 37-1 (methanol-moist) were initially introduced into a 0.7 l steel autoclave. After rinsing with nitrogen, 70 bar of hydrogen were forced in and the contents of the autoclave were heated to 100° C., while stirring. The hydrogen pressure was increased to 80 bar. After 50 minutes, the uptake of hydrogen had ended. The mixture was kept under the reaction conditions for a further 30 minutes. After cooling, letting down the hydrogen and removing the catalyst, the solvent was distilled off. Crude 2-amino-6-chlorophenyl-isopropylsulfane was already obtained as a 99% pure product (GC) which contained only 0.2% of 2-aminophenyl-isopropylsulfane (formed by dechlorination) and only 0.3% of m-chloroaniline (formed by desulfurization). The yield was 34.5 g. After rinsing with nitrogen, 70 bar of hydrogen The hydrogen pressure was increased to 80 bar The mixture was kept under the reaction conditions for a further 30 minutes After cooling removing the catalyst the solvent was distilled off

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 46.6 g of 2-chloro-6-nitrophenyl-isopropylsulfane, 160 ml of methanol and 5 g of Raney nickel 55 (water-moist, washed with methanol) were introduced into a steel autoclave. After flushing with nitrogen and hydrogen, the mixture was heated to 50° C., while stirring, and hydrogenation was carried out by forcing in hydrogen up to a maximum of 2 bar. After 2.5 hours, the uptake of hydrogen had ended. The mixture was then cooled to room temperature, the hydrogen was let down and the nickel catalyst was removed by filtration with suction and washed with methanol. After removal of the solvent, 39.9 g of 2-amino-6-chlorophenyl-isopropylsulfane were obtained in a purity of 97.8% (GC), which corresponds to 97% of theory. Only 0.2% of 2-aminophenylisopropylsulfane (formed by dehalogenation) was found as an impurity. Pure, colorless 2-amino-6-chlorophenyl-isopropylsulfane with a content of more than 99% was obtained by distillation at a boiling point of 144° C. at 11 mbar. After flushing with nitrogen and hydrogen The mixture was then cooled to room temperature the nickel catalyst was removed by filtration with suction washed with methanol After removal of the solvent

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 40 g of 2-chloro-6-nitrophenyl-isopropylsulfane, 160 g of methanol and 2.4 g of Raney nickel 37-1 (methanol-moist) were initially introduced into a 0.7 l steel autoclave. After rinsing with nitrogen, 70 bar of hydrogen were forced in and the contents of the autoclave were heated to 100° C., while stirring. The hydrogen pressure was increased to 80 bar. After 50 minutes, the uptake of hydrogen had ended. The mixture was kept under the reaction conditions for a further 30 minutes. After cooling, letting down the hydrogen and removing the catalyst, the solvent was distilled off. Crude 2-amino-6-chlorophenyl-isopropylsulfane was already obtained as a 99% pure product (GC) which contained only 0.2% of 2-aminophenyl-isopropylsulfane (formed by dechlorination) and only 0.3% of m-chloroaniline (formed by desulfurization). The yield was 34.5 g. After rinsing with nitrogen, 70 bar of hydrogen The hydrogen pressure was increased to 80 bar The mixture was kept under the reaction conditions for a further 30 minutes After cooling removing the catalyst the solvent was distilled off

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6 liters of dimethylformamide are added to 50 g of nickel chloride dihydrate, 200 g of BPPFA (1,1'-bisdiphenylphosphine-1-(dimethylaminoethyl)ferrocene) and 49 g of manganese powder, and the mixture is stirred at 50° C. for 2 hours under an inert atmosphere. A brown suspension forms. 1,200 g of 3-chloro-2-isopropylthioaniline and 430 g of KCN are added to the suspension and the mixture is stirred for 16 hours at 50° C. After working up, white crystals of m.p. 82° C. are obtained in a yield of approximately 90%. the mixture is stirred for 16 hours at 50° C white crystals of m.p. 82° C. are obtained in a yield of approximately 90%

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 40 g of 2-chloro-6-nitrophenyl-isopropylsulfane, 160 g of methanol and 2.4 g of Raney nickel 37-1 (methanol-moist) were initially introduced into a 0.7 l steel autoclave. After rinsing with nitrogen, 70 bar of hydrogen were forced in and the contents of the autoclave were heated to 100° C., while stirring. The hydrogen pressure was increased to 80 bar. After 50 minutes, the uptake of hydrogen had ended. The mixture was kept under the reaction conditions for a further 30 minutes. After cooling, letting down the hydrogen and removing the catalyst, the solvent was distilled off. Crude 2-amino-6-chlorophenyl-isopropylsulfane was already obtained as a 99% pure product (GC) which contained only 0.2% of 2-aminophenyl-isopropylsulfane (formed by dechlorination) and only 0.3% of m-chloroaniline (formed by desulfurization). The yield was 34.5 g. After rinsing with nitrogen, 70 bar of hydrogen The hydrogen pressure was increased to 80 bar The mixture was kept under the reaction conditions for a further 30 minutes After cooling removing the catalyst the solvent was distilled off