(3-chloro-2-oxopropyl) acetate

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: 1-Chloro-3-acetoxyacetone (15.05 g.) is dissolved in tetrahydrofuran (50 ml.) and water (25 ml.) is added. Sodium azide (8.7 g.) is added and the mixture is allowed to stir overnight at room temperature. The reaction mixture is diluted with ether (200 ml.) and the aqueous phase is separated. The organic phase is washed once with brine, then dried and evaporated to give 1-azido-3-acetoxyacetone. the aqueous phase is separated The organic phase is washed once with brine dried evaporated

反応条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Sodium hydride (4.5 g.; 57% in mineral oil) is placed under a nitrogen atmosphere and the mineral oil removed with petroleum ether. Dimethylsulfoxide (30 ml.) is then added and the mixture is stirred at 70° C. for two hours and then cooled to 10° C. Methyltriphenylphosphonium bromide (35.7 g.) dissolved in dimethylsulfoxide (50 ml.) is added dropwise under nitrogen to afford a yellowish-orange ylide solution. 1-Chloro-3-acetoxy-2-propanone (15 g.) in dimethylsulfoxide (20 ml.) is then added and the reaction mixture is stirred until the color of the ylide disappears and then is stirred an additional hour at room temperature. The reaction mixture is dissolved in hexane (200 ml.) and washed three times with water. The organic phase is filtered to remove triphenylphosphine oxide and then dried over magnesium sulfate. The solvent is evaporated and the residue is distilled under vacuum to afford 1-chloro-2-methylene-3-acetoxypropane. the mineral oil removed with petroleum ether Dimethylsulfoxide (30 ml.) is then added cooled to 10° C Methyltriphenylphosphonium bromide (35.7 g.) dissolved in dimethylsulfoxide (50 ml.) is added dropwise under nitrogen to afford a yellowish-orange ylide solution the reaction mixture is stirred until the color of the ylide is stirred an additional hour at room temperature washed three times with water The organic phase is filtered to remove triphenylphosphine oxide dried over magnesium sulfate The solvent is evaporated the residue is distilled under vacuum

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

実験手順: 1-Chloro-3-acetoxyacetone (15.05 g.) is dissolved in tetrahydrofuran (50 ml.) and water (25 ml.) is added. Sodium azide (8.7 g.) is added and the mixture is allowed to stir overnight at room temperature. The reaction mixture is diluted with ether (200 ml.) and the aqueous phase is separated. The organic phase is washed once with brine, then dried and evaporated to give 1-azido-3-acetoxyacetone. the aqueous phase is separated The organic phase is washed once with brine dried evaporated

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

実験手順: 1-Chloro-3-acetoxyacetone (15.05 g.) is dissolved in tetrahydrofuran (50 ml.) and water (25 ml.) is added. Sodium azide (8.7 g.) is added and the mixture is allowed to stir overnight at room temperature. The reaction mixture is diluted with ether (200 ml.) and the aqueous phase is separated. The organic phase is washed once with brine, then dried and evaporated to give 1-azido-3-acetoxyacetone. the aqueous phase is separated The organic phase is washed once with brine dried evaporated

反応条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Sodium hydride (4.5 g.; 57% in mineral oil) is placed under a nitrogen atmosphere and the mineral oil removed with petroleum ether. Dimethylsulfoxide (30 ml.) is then added and the mixture is stirred at 70° C. for two hours and then cooled to 10° C. Methyltriphenylphosphonium bromide (35.7 g.) dissolved in dimethylsulfoxide (50 ml.) is added dropwise under nitrogen to afford a yellowish-orange ylide solution. 1-Chloro-3-acetoxy-2-propanone (15 g.) in dimethylsulfoxide (20 ml.) is then added and the reaction mixture is stirred until the color of the ylide disappears and then is stirred an additional hour at room temperature. The reaction mixture is dissolved in hexane (200 ml.) and washed three times with water. The organic phase is filtered to remove triphenylphosphine oxide and then dried over magnesium sulfate. The solvent is evaporated and the residue is distilled under vacuum to afford 1-chloro-2-methylene-3-acetoxypropane. the mineral oil removed with petroleum ether Dimethylsulfoxide (30 ml.) is then added cooled to 10° C Methyltriphenylphosphonium bromide (35.7 g.) dissolved in dimethylsulfoxide (50 ml.) is added dropwise under nitrogen to afford a yellowish-orange ylide solution the reaction mixture is stirred until the color of the ylide is stirred an additional hour at room temperature washed three times with water The organic phase is filtered to remove triphenylphosphine oxide dried over magnesium sulfate The solvent is evaporated the residue is distilled under vacuum

反応条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Sodium hydride (4.5 g.; 57% in mineral oil) is placed under a nitrogen atmosphere and the mineral oil removed with petroleum ether. Dimethylsulfoxide (30 ml.) is then added and the mixture is stirred at 70° C. for two hours and then cooled to 10° C. Methyltriphenylphosphonium bromide (35.7 g.) dissolved in dimethylsulfoxide (50 ml.) is added dropwise under nitrogen to afford a yellowish-orange ylide solution. 1-Chloro-3-acetoxy-2-propanone (15 g.) in dimethylsulfoxide (20 ml.) is then added and the reaction mixture is stirred until the color of the ylide disappears and then is stirred an additional hour at room temperature. The reaction mixture is dissolved in hexane (200 ml.) and washed three times with water. The organic phase is filtered to remove triphenylphosphine oxide and then dried over magnesium sulfate. The solvent is evaporated and the residue is distilled under vacuum to afford 1-chloro-2-methylene-3-acetoxypropane. the mineral oil removed with petroleum ether Dimethylsulfoxide (30 ml.) is then added cooled to 10° C Methyltriphenylphosphonium bromide (35.7 g.) dissolved in dimethylsulfoxide (50 ml.) is added dropwise under nitrogen to afford a yellowish-orange ylide solution the reaction mixture is stirred until the color of the ylide is stirred an additional hour at room temperature washed three times with water The organic phase is filtered to remove triphenylphosphine oxide dried over magnesium sulfate The solvent is evaporated the residue is distilled under vacuum

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

実験手順: A solution of methyl cyanoacetate (1.18 mL, 13.28 mmol) and sodium sulfide nonahydrate (3.20 g, 13.28 mmol) in methanol (25 mL) at 0° C. was treated with 1-acetoxy-3-chloroacetone (2.0 g, 13.28 mmol). The cold bath was removed and triethylamine (1.86 mL, 13.28 mmol) was added dropwise. The solution was stirred at room temperature for 20 hours then diluted with water and extracted into ethyl acetate. The organic layer was dried over sodium sulfate, filtered, and the solvent removed under vacuum to provide the titled compound (1.25 g, 51%). MS (DCI/NH3) M/Z 188 (M+H)+; 1H NMR (300 MHz, DMSO-d6) δ 3.68 (s, 3 H) 4.45 (dd, J=5.52, 1.47 Hz, 2 H) 4.88 (t, J=5.70 Hz, 1 H) 6.12 (s, 1 H) 7.28 (s, 2 H) The cold bath was removed extracted into ethyl acetate The organic layer was dried over sodium sulfate filtered the solvent removed under vacuum

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

実験手順: A solution of methyl cyanoacetate (1.18 mL, 13.28 mmol) and sodium sulfide nonahydrate (3.20 g, 13.28 mmol) in methanol (25 mL) at 0° C. was treated with 1-acetoxy-3-chloroacetone (2.0 g, 13.28 mmol). The cold bath was removed and triethylamine (1.86 mL, 13.28 mmol) was added dropwise. The solution was stirred at room temperature for 20 hours then diluted with water and extracted into ethyl acetate. The organic layer was dried over sodium sulfate, filtered, and the solvent removed under vacuum to provide the titled compound (1.25 g, 51%). MS (DCI/NH3) M/Z 188 (M+H)+; 1H NMR (300 MHz, DMSO-d6) δ 3.68 (s, 3 H) 4.45 (dd, J=5.52, 1.47 Hz, 2 H) 4.88 (t, J=5.70 Hz, 1 H) 6.12 (s, 1 H) 7.28 (s, 2 H) The cold bath was removed extracted into ethyl acetate The organic layer was dried over sodium sulfate filtered the solvent removed under vacuum