1-nitropropan-2-one

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: 1.5 g (10 mmol) of 2-chlorobenzaldehyde are boiled with 1.03 g (10 mmol) of nitroacetone, 2.7 g (20 mmol) of phenylacetone and 0.7 g (10 mmol) of ammonium acetate in 20 ml of ethanol overnight. The mixture is concentrated, the residue is taken up in ethyl acetate, and the solution is washed with water, dried and concentrated. The residue from evaporation is purified on a silica gel column using toluene/ethyl acetate 10:1. The fractions containing product are collected and concentrated. The substance crystallizes using ether. It is filtered off with suction and washed with ether. 200 mg of orange-colored crystals, of melting point 232° C., are obtained. The mixture is concentrated the solution is washed with water dried concentrated The residue from evaporation is purified on a silica gel column The fractions containing product are collected concentrated The substance crystallizes It is filtered off with suction washed with ether

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

実験手順: 12.82 g (50 mmol) of 1-(3-chlorophenyl)-2-phenyl-3-oxo-1-butene in 75 ml of ethanol are heated under reflux with 5.15 g (50 mmol) of nitroacetone and 3.85 g (50 mmol) of ammonium acetate for 16 hours. A further 5.15 g of nitroacetone and 3.85 g of ammonium acetate are added and the mixture is boiled for 24 hours, and 5.15 g of nitroacetone and 3.85 g of ammonium acetate are added and the mixture is boiled for 24 hours. It is cooled and concentrated, the residue is taken up in ethyl acetate, and the solution is extracted by shaking twice with water, dried and concentrated. the mixture is boiled for 24 hours It is cooled concentrated the solution is extracted dried concentrated

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

実験手順: 15.1 g (0.1 mol) of 3-nitrobenzaldehyde, together with 16.9 g (0.1 mol) of cyclopentyl β-aminocrotonate and 10.3 g (0.1 mol) of nitroacetone in 150 ml of ethanol, were heated under reflux for 6 hours. After the reaction mixture had cooled, the solvent was distilled off in vacuo, and the oily residue was taken up in a small amount of chloroform and was chromatographed on a silica gel column, using chloroform with the addition of methanol. The fractions containing the reaction product were concentrated, the residue was taken up in a small amount of isopropanol, and the nitrodihydropyridine crystallized in yellow crystals of melting point 174° C. under reflux for 6 hours After the reaction mixture had cooled the solvent was distilled off in vacuo was chromatographed on a silica gel column with the addition of methanol The fractions containing the reaction product were concentrated the nitrodihydropyridine crystallized in yellow crystals of melting point 174° C.

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

実験手順: 10 mmoles of 2-benzylmercaptobenzaldehyde, 15 mmoles of nitroacetone and 10 mmoles of 3-aminocrotonic acid N-[4-(6-oxo-1,4,5,6-tetrahydropyridazin-3-yl)-phenyl]-amide in 30 ml of isopropanol are heated at 60°-70° C. for 10 hours. The reaction mixture is concentrated and the residue is taken up in chloroform and chromatographed over silica gel using chloroform to which methanol is added. The product is recrystallized from isopropanol. The reaction mixture is concentrated chromatographed over silica gel is added The product is recrystallized from isopropanol

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

実験手順: 10 mmoles of 2-benzylmercaptobenzaldehyde, 15 mmoles of nitroacetone and 10 mmoles of 3-aminocrotonic acid N-[4-(6-oxo-1,4,5,6-tetrahydropyridazin-3-yl)-phenyl]-amide in 30 ml of isopropanol are heated at 60°-70° C. for 10 hours. The reaction mixture is concentrated and the residue is taken up in chloroform and chromatographed over silica gel using chloroform to which methanol is added. The product is recrystallized from isopropanol. The reaction mixture is concentrated chromatographed over silica gel is added The product is recrystallized from isopropanol

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

実験手順: 28.1 g (200 mmol) of 2-chlorobenzaldehyde are boiled under reflux with 37.4 g (200 mmol) of 2-acetoxyethyl β-aminocrotonate and 32.6 g (320 mmol) of nitroacetone in 400 ml of ethanol for 4 hours. The mixture is cooled and concentrated. The evaporation residue is taken up in ethyl acetate and the mixture is washed with water, sodium bicarbonate solution and water again, dried and concentrated. The semi-solid evaporation residue is stirred with ethanol, filtered off with suction and washed with ethanol. 23.2 g (29.4% of theory) of a yellow-colored product of melting point 158°-160° C. are obtained. The mixture is cooled concentrated the mixture is washed with water, sodium bicarbonate solution and water again dried concentrated The semi-solid evaporation residue filtered off with suction washed with ethanol 23.2 g (29.4% of theory) of a yellow-colored product of melting point 158°-160° C. are obtained

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

実験手順: To a 2 liter 4-neck round-bottom flask fitted with mechanical stirrer and thermowell, under a nitrogen atmosphere, was added 138.2 g of N-{2-[(4-chlorobutyl)thio]phenylmethylene}-1-butanamine and 350 ml of benzene, followed by 91.9 ml of acetic anhydride. The mixture was cooled in an ice water bath as 50.18 g of nitroacetone was added. The bath was permitted to warm to room temperature and the reaction stirred overnight. The solvent was removed by rotary evaporation and the product was partitioned between ether and sodium bicarbonate. The organic layer was washed with brine, dried over magnesium sulfate and concentrated to dryness. Purification via column chromatograph on silica gel, eluting with 15% ethyl acetate in hexane provided the product as a pale orange oil. Mass spectrum: 314 (M+1). To a 2 liter 4-neck round-bottom flask fitted with mechanical stirrer was added The solvent was removed by rotary evaporation the product was partitioned between ether and sodium bicarbonate The organic layer was washed with brine dried over magnesium sulfate concentrated to dryness Purification via column chromatograph on silica gel eluting with 15% ethyl acetate in hexane

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

実験手順: To a 2 liter 4-neck round-bottom flask fitted with mechanical stirrer and thermowell, under a nitrogen atmosphere, was added 138.2 g of N-{2-[(4-chlorobutyl)thio]phenylmethylene}-1-butanamine and 350 ml of benzene, followed by 91.9 ml of acetic anhydride. The mixture was cooled in an ice water bath as 50.18 g of nitroacetone was added. The bath was permitted to warm to room temperature and the reaction stirred overnight. The solvent was removed by rotary evaporation and the product was partitioned between ether and sodium bicarbonate. The organic layer was washed with brine, dried over magnesium sulfate and concentrated to dryness. Purification via column chromatograph on silica gel, eluting with 15% ethyl acetate in hexane provided the product as a pale orange oil. Mass spectrum: 314 (M+1). To a 2 liter 4-neck round-bottom flask fitted with mechanical stirrer was added The solvent was removed by rotary evaporation the product was partitioned between ether and sodium bicarbonate The organic layer was washed with brine dried over magnesium sulfate concentrated to dryness Purification via column chromatograph on silica gel eluting with 15% ethyl acetate in hexane

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Diethyl ethoxymethyleneoxalacetate (150.4 g, 0.616 mol, 1 eq) is dissolved in 300 mL absolute ethanol under a nitrogen atmosphere and the mixture is cooled to -10° C. in an ice/acetone bath. Unpurified 1-nitro-2-propanone (prepared by the method of D. Baker and S. Putt, Synthesis, 1978, 478-9, assumed to be 63.448 g, 0.616 mol) dissolved in 100 mL absolute ethanol is then added to the stirred solution. Sodium acetate (101.06 g, 1.232 mol) is then added in portions so that the temperature of the reaction remains below 10° C., followed by the addition of ammonium acetate (94.6 g, 1.232 g). The reaction mixture is allowed to warm to room temperature and is then stirred for 16 hours. The mixture is filtered through two pads of silica gel which are then eluted with methylene chloride. The filtrate is concentrated in vacuo to a thick dark oil which is chromatographed using hexanes as eluant, yielding the product in an 18.2% yield (31.4 g), having a melting point 90°-91.5° C. Putt, Synthesis, 1978, 478-9 is then added to the stirred solution remains below 10° C. to warm to room temperature The mixture is filtered through two pads of silica gel which are then eluted with methylene chloride The filtrate is concentrated in vacuo to a thick dark oil which is chromatographed yielding the product in an 18.2% yield (31.4 g)

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Diethyl ethoxymethyleneoxalacetate (150.4 g, 0.616 mol, 1 eq) is dissolved in 300 mL absolute ethanol under a nitrogen atmosphere and the mixture is cooled to -10° C. in an ice/acetone bath. Unpurified 1-nitro-2-propanone (prepared by the method of D. Baker and S. Putt, Synthesis, 1978, 478-9, assumed to be 63.448 g, 0.616 mol) dissolved in 100 mL absolute ethanol is then added to the stirred solution. Sodium acetate (101.06 g, 1.232 mol) is then added in portions so that the temperature of the reaction remains below 10° C., followed by the addition of ammonium acetate (94.6 g, 1.232 g). The reaction mixture is allowed to warm to room temperature and is then stirred for 16 hours. The mixture is filtered through two pads of silica gel which are then eluted with methylene chloride. The filtrate is concentrated in vacuo to a thick dark oil which is chromatographed using hexanes as eluant, yielding the product in an 18.2% yield (31.4 g), having a melting point 90°-91.5° C. Putt, Synthesis, 1978, 478-9 is then added to the stirred solution remains below 10° C. to warm to room temperature The mixture is filtered through two pads of silica gel which are then eluted with methylene chloride The filtrate is concentrated in vacuo to a thick dark oil which is chromatographed yielding the product in an 18.2% yield (31.4 g)