N-(2,2,6,6-tetramethylpiperidin-4-yl)acetamide

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

実験手順: Acetic anhydride (70 g, 0.686 mol) was added dropwis to an ice cooled solution of 4-Amino-2,2,6,6-Tetramethyl-piperidin (34.6 g. 0.221 mol) in ether (100 ml). After the addition was complete (about 1 h), the reaction mixture was stirred for 30 minutes at room temperature. The precipitated white product, 4-acetylamino-2,2,6,6-Tetramethyl-piperidin (55.6 g, 98%) was filtered off and washed with ether and air dried. m.p. 175° C. subl. After the addition (about 1 h) The precipitated white product, 4-acetylamino-2,2,6,6-Tetramethyl-piperidin (55.6 g, 98%) was filtered off washed with ether and air dried

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

実験手順: Acetic anhydride (70 g, 0.686 mol) was added dropwis to an ice cooled solution of 4-Amino-2,2,6,6-Tetramethyl-piperidin (34.6 g. 0.221 mol) in ether (100 ml). After the addition was complete (about 1 h), the reaction mixture was stirred for 30 minutes at room temperature. The precipitated white product, 4-acetylamino-2,2,6,6-Tetramethyl-piperidin (55.6 g, 98%) was filtered off and washed with ether and air dried. m.p. 175° C. subl. After the addition (about 1 h) The precipitated white product, 4-acetylamino-2,2,6,6-Tetramethyl-piperidin (55.6 g, 98%) was filtered off washed with ether and air dried

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A two-phase mixture of 260 grams (2.02 mol) of 70% aqueous tert-butyl hydroperoxide, 350 ml of n-octane, and 50 grams of sodium chloride is vigorously stirred. The organic phase is separated, dried over anhydrous magnesium sulfate and filtered. The filtrate is diluted with n-octane to a volume of 580 ml. To a mixture of 100.0 grams (0.504 mol) of N-(2,2,6,6-tetramethylpiperidin-4-yl)acetamide, 1.8 gram of molybdenum trioxide, and 100 ml of n-octane preheated to 120° C. is added 300 ml of tert-butyl hydroperoxide solution over a 15-minute period. The mixture quickly turns red and water is collected in a Dean-Stark trap. The remaining tert-butyl hydroperoxide solution (280 ml) is added to-the refluxing reaction mixture over a period of 2.5 hours. The reaction mixture is heated at reflux for three hours after the addition is complete, then treated with 50.1 grams (0.50 mol) of 90% tert-butyl hydroperoxide and heated at reflux for 2.5 hours to discharge the red color of the N-oxyl intermediate. Solids are removed by filtration, and the filtrate is cooled to 5° C. and stirred with a solution of 40 grams of sodium sulfite in 400 ml of water to decompose unreacted hydroperoxide. The organic layer is dried over anhydrous magnesium sulfate and concentrated to an oil. Purification by flash chromatography (1:1 heptane:ethyl acetate) affords 100.2 grams (61% yield) of the title compound as a waxy solid. The organic phase is separated dried over anhydrous magnesium sulfate filtered The filtrate is diluted with n-octane to a volume of 580 ml preheated to 120° C. The mixture quickly turns red and water is collected in a Dean-Stark trap The remaining tert-butyl hydroperoxide solution (280 ml) is added to-the refluxing reaction mixture over a period of 2.5 hours The reaction mixture is heated at reflux for three hours after the addition heated at reflux for 2.5 hours Solids are removed by filtration stirred with a solution of 40 grams of sodium sulfite in 400 ml of water The organic layer is dried over anhydrous magnesium sulfate concentrated to an oil Purification by flash chromatography (1:1 heptane:ethyl acetate)

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

実験手順: A solution of 100.0 grams (64 mmol) of 4-amino-2,2,6,6-tetramethylpiperidine in 150 ml of toluene and a solution of 65.4 grams (64 mmol) of acetic anhydride in 175 ml of toluene are simultaneously added over a 45-minute period to a flask containing 150 ml of toluene. The reaction temperature is maintained at 25°-35° C. by using an ice water bath. The reaction mixture is stirred for 30 minutes after the addition is complete. Solids are separated by filtration, washed with ether and dissolved in 500 ml of water. This aqueous solution is added to a solution of 28 grams of sodium hydroxide in 100 ml of water. A crude solid is isolated by filtration and the filtrate is saturated with solid sodium chloride to precipitate more of the product. The solids are combined, dried and dissolved in warm isopropanol. The alcohol solution is filtered to remove salts, and the filtrate is concentrated to give an oil. The oil is crystallized from heptane to afford 111.0 grams (87% yield) of the title compound as a white solid melting at 100°-102° C. The reaction temperature is maintained at 25°-35° C. after the addition Solids are separated by filtration washed with ether dissolved in 500 ml of water This aqueous solution is added to a solution of 28 grams of sodium hydroxide in 100 ml of water A crude solid is isolated by filtration to precipitate more of the product dried dissolved in warm isopropanol The alcohol solution is filtered to remove salts the filtrate is concentrated to give an oil The oil is crystallized from heptane

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A two-phase mixture of 260 grams (2.02 mol ) of 70% aqueous tert-butyl hydroperoxide, 350 ml of n-octane, and 50 grams of sodium chloride is vigorously stirred. The organic phase is separated, dried over anhydrous magnesium sulfate and filtered. The filtrate is diluted with n-octane to a volumne of 580 ml. To a mixture of 100.0 grams (0.504 mol) of N-(2,2,6,6-tetramethylpiperidin-4-yl)acetamide, 1.8 gram of molybdenum trioxide, and 100 ml of n-octane preheated to 120° C. is added 300 ml of tert-butyl hydroperoxide solution over a 15-minute period. The mixture quickly turns red and water is collected in a Dean-Stark trap. The remaining tert-butyl hydroperoxide solution (280 ml) is added to-the refluxing reaction mixture over a period of 2.5 hours. The reaction mixture is heated at reflux for three hours after the addition is complete, then treated with 50.1 grams (0.50 mol ) of 90% tert-butyl hydroperoxide and heated at reflux for 2.5 hours to discharge the red color of the N-oxyl intermediate. Solids are removed by filtration, and the filtrate is cooled to 5° C. and stirred with a solution of 40 grams of sodium sulfite in 400 ml of water to decompose unreacted hydroperoxide. The organic layer is dried over anhydrous magnesium sulfate and concentrated to an oil. Purification by flash chromatography (1:1 heptane:ethyl acetate) affords 100.2 grams (61% yield) of the title compound as a waxy solid. The organic phase is separated dried over anhydrous magnesium sulfate filtered The filtrate is diluted with n-octane to a volumne of 580 ml preheated to 120° C. The mixture quickly turns red and water is collected in a Dean-Stark trap The remaining tert-butyl hydroperoxide solution (280 ml) is added to-the refluxing reaction mixture over a period of 2.5 hours The reaction mixture is heated at reflux for three hours after the addition heated at reflux for 2.5 hours Solids are removed by filtration stirred with a solution of 40 grams of sodium sulfite in 400 ml of water The organic layer is dried over anhydrous magnesium sulfate concentrated to an oil Purification by flash chromatography (1:1 heptane:ethyl acetate)

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

実験手順: A solution of 100.0 grams (64 mmol) of 4-amino-2,2,6,6-tetramethylpiperidine in 150 ml of toluene and a solution of 65.4 grams (64 mmol) of acetic anhydride in 175 ml of toluene are simultaneously added over a 45-minute period to a flask containing 150 ml of toluene. The reaction temperature is maintained at 25°-35° C. by using an ice water bath. The reaction mixture is stirred for 30 minutes after the addition is complete. Solids are separated by filtration, washed with ether and dissolved in 500 ml of water. This aqueous solution is added to a solution of 28 grams of sodium hydroxide in 100 ml of water. A crude solid is isolated by filtration and the filtrate is saturated with solid sodium chloride to precipitate more of the product. The solids are combined, dried and dissolved in warm isopropanol. The alcohol solution is filtered to remove salts, and the filtrate is concentrated to give an oil. The oil is crystallized from heptane to afford 111.0 grams (87% yield) of the title compound as a white solid melting at 100°-102° C. The reaction temperature is maintained at 25°-35° C. after the addition Solids are separated by filtration washed with ether dissolved in 500 ml of water This aqueous solution is added to a solution of 28 grams of sodium hydroxide in 100 ml of water A crude solid is isolated by filtration to precipitate more of the product dried dissolved in warm isopropanol The alcohol solution is filtered to remove salts the filtrate is concentrated to give an oil The oil is crystallized from heptane

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A two-phase mixture of 260 grams (2.02 mol) of 70% aqueous tert-butyl hydroperoxide, 350 ml of n-octane, and 50 grams of sodium chloride is vigorously stirred. The organic phase is separated, dried over anhydrous magnesium sulfate and filtered. The filtrate is diluted with n-octane to a volumne of 580 ml. To a mixture of 100.0 grams (0.504 mol) of N-(2,2,6,6-tetramethylpiperidin-4-yl)acetamide, 1.8 gram of molybdenum trioxide, and 100 ml of n-octane preheated to 120° C. is added 300 ml of tert-butyl hydroperoxide solution over a 15-minute period. The mixture quickly turns red and water is collected in a Dean-Stark trap. The remaining tert-butyl hydroperoxide solution (280 ml) is added to-the refluxing reaction mixture over a period of 2.5 hours. The reaction mixture is heated at reflux for three hours after the addition is complete, then treated with 50.1 grams (0.50 mol) of 90% tert-butyl hydroperoxide and heated at reflux for 2.5 hours to discharge the red color of the N-oxyl intermediate. Solids are removed by filtration, and the filtrate is cooled to 5° C. and stirred with a solution of 40 grams of sodium sulfite in 400 ml of water to decompose unreacted hydroperoxide. The organic layer is dried over anhydrous magnesium sulfate and concentrated to an oil. Purification by flash chromatography (1:1 heptane:ethyl acetate) affords 100.2 grams (61% yield) of the title compound as a waxy solid. The organic phase is separated dried over anhydrous magnesium sulfate filtered The filtrate is diluted with n-octane to a volumne of 580 ml preheated to 120° C. The mixture quickly turns red and water is collected in a Dean-Stark trap The remaining tert-butyl hydroperoxide solution (280 ml) is added to-the refluxing reaction mixture over a period of 2.5 hours The reaction mixture is heated at reflux for three hours after the addition heated at reflux for 2.5 hours Solids are removed by filtration stirred with a solution of 40 grams of sodium sulfite in 400 ml of water The organic layer is dried over anhydrous magnesium sulfate concentrated to an oil Purification by flash chromatography (1:1 heptane:ethyl acetate)

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

実験手順: A solution of 100.0 grams (64 mmol) of 4-amino-2,2,6,6-tetramethylpiperidine in 150 ml of toluene and a solution of 65.4 grams (64 mmol) of acetic anhydride in 175 ml of toluene are simultaneously added over a 45-minute period to a flask containing 150 ml of toluene. The reaction temperature is maintained at 25°-35° C. by using an ice water bath. The reaction mixture is stirred for 30 minutes after the addition is complete. Solids are separated by filtration, washed with ether and dissolved in 500 ml of water. This aqueous solution is added to a solution of 28 grams of sodium hydroxide in 100 ml of water. A crude solid is isolated by filtration and the filtrate is saturated with solid sodium chloride to precipitate more of the product. The solids are combined, dried and dissolved in warm isopropanol. The alcohol solution is filtered to remove salts, and the filtrate is concentrated to give an oil. The oil is crystallized from heptane to afford 111.0 grams (87% yield) of the title compound as a white solid melting at 100°-102° C. The reaction temperature is maintained at 25°-35° C. after the addition Solids are separated by filtration washed with ether dissolved in 500 ml of water This aqueous solution is added to a solution of 28 grams of sodium hydroxide in 100 ml of water A crude solid is isolated by filtration to precipitate more of the product dried dissolved in warm isopropanol The alcohol solution is filtered to remove salts the filtrate is concentrated to give an oil The oil is crystallized from heptane

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A two-phase mixture of 260 grams (2.02 mol) of 70% aqueous tert-butyl hydroperoxide, 350 ml of n-octane, and 50 grams of sodium chloride is vigorously stirred. The organic phase is separated, dried over anhydrous magnesium sulfate and filtered. The filtrate is diluted with n-octane to a volume of 580 ml. To a mixture of 100.0 grams (0.504 mol) of N-(2,2,6,6-tetramethylpiperidin-4-yl)acetamide, 1.8 gram of molybdenum trioxide, and 100 ml of n-octane preheated to 120° C. is added 300 ml of tert-butyl hydroperoxide solution over a 15-minute period. The mixture quickly turns red and water is collected in a Dean-Stark trap. The remaining tert-butyl hydroperoxide solution (280 ml) is added to-the refluxing reaction mixture over a period of 2.5 hours. The reaction mixture is heated at reflux for three hours after the addition is complete, then treated with 50.1 grams (0.50 mol) of 90% tert-butyl hydroperoxide and heated at reflux for 2.5 hours to discharge the red color of the N-oxyl intermediate. Solids are removed by filtration, and the filtrate is cooled to 5° C. and stirred with a solution of 40 grams of sodium sulfite in 400 ml of water to decompose unreacted hydroperoxide. The organic layer is dried over anhydrous magnesium sulfate and concentrated to an oil. Purification by flash chromatography (1:1 heptane:ethyl acetate) affords 100.2 grams (61% yield) of the title compound as a waxy solid. The organic phase is separated dried over anhydrous magnesium sulfate filtered The filtrate is diluted with n-octane to a volume of 580 ml preheated to 120° C. The mixture quickly turns red and water is collected in a Dean-Stark trap The remaining tert-butyl hydroperoxide solution (280 ml) is added to-the refluxing reaction mixture over a period of 2.5 hours The reaction mixture is heated at reflux for three hours after the addition heated at reflux for 2.5 hours Solids are removed by filtration stirred with a solution of 40 grams of sodium sulfite in 400 ml of water The organic layer is dried over anhydrous magnesium sulfate concentrated to an oil Purification by flash chromatography (1:1 heptane:ethyl acetate)

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

実験手順: A solution of 100.0 grams (64 mmol) of 4-amino-2,2,6,6-tetramethylpiperidine in 150 ml of toluene and a solution of 65.4 grams (64 mmol) of acetic anhydride in 175 ml of toluene are simultaneously added over a 45-minute period to a flask containing 150 ml of toluene. The reaction temperature is maintained at 25°-35° C. by using an ice water bath. The reaction mixture is stirred for 30 minutes after the addition is complete. Solids are separated by filtration, washed with ether and dissolved in 500 ml of water. This aqueous solution is added to a solution of 28 grams of sodium hydroxide in 100 ml of water. A crude solid is isolated by filtration and the filtrate is saturated with solid sodium chloride to precipitate more of the product. The solids are combined, dried and dissolved in warm isopropanol. The alcohol solution is filtered to remove salts, and the filtrate is concentrated to give an oil. The oil is crystallized from heptane to afford 111.0 grams (87% yield) of the title compound as a white solid melting at 100°-102° C. The reaction temperature is maintained at 25°-35° C. after the addition Solids are separated by filtration washed with ether dissolved in 500 ml of water This aqueous solution is added to a solution of 28 grams of sodium hydroxide in 100 ml of water A crude solid is isolated by filtration to precipitate more of the product dried dissolved in warm isopropanol The alcohol solution is filtered to remove salts the filtrate is concentrated to give an oil The oil is crystallized from heptane

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A two-phase mixture of 260 grams (2.02 tool) of 70% aqueous tert-butyl hydroperoxide, 350 ml of n-octane, and 50 grams of sodium chloride is vigorously stirred. The organic phase is separated, dried over anhydrous magnesium sulfate and filtered. The filtrate is diluted with n-octane to a volumne of 580 ml. To a mixture of 100.0 grams (0.504 mol) of N-(2,2,6,6-tetramethylpiperidin-4-yl)acetamide, 1.8 gram of molybdenum trioxide, and 100 ml of n-octane preheated to 120° C. is added 300 ml of tert-butyl hydroperoxide solution over a 15-minute period. The mixture quickly turns red and water is collected in a Dean-Stark trap. The remaining tert-butyl hydroperoxide solution (280 ml) is added to-the refluxing reaction mixture over a period of 2.5 hours. The reaction mixture is heated at reflux for three hours after the addition is complete, then treated with 50.1 grams (0.50 tool) of 90% tert-butyl hydroperoxide and heated at reflux for 2.5 hours to discharge the red color of the N-oxyl intermediate. Solids are removed by filtration, and the filtrate is cooled to 5° C. and stirred with a solution of 40 grams of sodium sulfite in 400 ml of water to decompose unreacted hydroperoxide. The organic layer is dried over anhydrous magnesium sulfate and concentrated to an oil. Purification by flash chromatography (1:1 heptane:ethyl acetate) affords 100.2 grams (61% yield) of the title compound as a waxy solid. The organic phase is separated dried over anhydrous magnesium sulfate filtered The filtrate is diluted with n-octane to a volumne of 580 ml preheated to 120° C. The mixture quickly turns red and water is collected in a Dean-Stark trap The remaining tert-butyl hydroperoxide solution (280 ml) is added to-the refluxing reaction mixture over a period of 2.5 hours The reaction mixture is heated at reflux for three hours after the addition heated at reflux for 2.5 hours Solids are removed by filtration stirred with a solution of 40 grams of sodium sulfite in 400 ml of water The organic layer is dried over anhydrous magnesium sulfate concentrated to an oil Purification by flash chromatography (1:1 heptane:ethyl acetate)

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

実験手順: A solution of 100.0 grams (64 mmol) of 4-amino-2,2,6,6-tetramethylpiperidine in 150 ml of toluene and a solution of 65.4 grams (64 mmol) of acetic anhydride in 175 ml of toluene are simultaneously added over a 45-minute period to a flask containing 150 ml of toluene. The reaction temperature is maintained at 25°-35° C. by using an ice water bath. The reaction mixture is stirred for 30 minutes after the addition is complete. Solids are separated by filtration, washed with ether and dissolved in 500 ml of water. This aqueous solution is added to a solution of 28 grams of sodium hydroxide in 100 ml of water. A crude solid is isolated by filtration and the filtrate is saturated with solid sodium chloride to precipitate more of the product. The solids are combined, dried and dissolved in warm isopropanol. The alcohol solution is filtered to remove salts, and the filtrate is concentrated to give an oil. The oil is crystallized from heptane to afford 111.0 grams (87% yield) of the title compound as a white solid melting at 100°-102° C. The reaction temperature is maintained at 25°-35° C. after the addition Solids are separated by filtration washed with ether dissolved in 500 ml of water This aqueous solution is added to a solution of 28 grams of sodium hydroxide in 100 ml of water A crude solid is isolated by filtration to precipitate more of the product dried dissolved in warm isopropanol The alcohol solution is filtered to remove salts the filtrate is concentrated to give an oil The oil is crystallized from heptane