3-(4-chlorophenyl)prop-2-enenitrile

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: 0.7 g (0.015 mol) sodiumhydride (55%) were added to a solution of 1.50 g (0.005 mol) 3-benzenesulfonylmethyl-5-furan-2-yl-1H-[1,2,4]triazole in 50 ml tetrahydrofuran. The mixture was refluxed and 0.85 g (0.005 mol) 3-(4-chlorophenyl)-2-propenenitrile in 30 ml tetrahydrofuran were added during, aperiod of 5.5 hours. Boiling was continued for 30 minutes and then 20 ml methanol were added at room temperature. Evaporation of the solvent and chromatography on silicagel with dichloromethane/methanol 99/1 gave 0.57 g (35%) 7-(4-chloro-phenyl)-2-furan-2-yl-[1,2,4]triazolo[1,5-a]pyridin-5-ylamine as pale crystals. MS m/e (%): 311 (M+H+, 100). The mixture was refluxed Evaporation of the solvent and chromatography on silicagel with dichloromethane/methanol 99/1

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

実験手順: 0.7 g (0.015 mol) sodiumhydride (55%) were added to a solution of 1.50 g (0.005 mol) 3-benzenesulfonylmethyl-5-furan-2-yl-1H-[1,2,4]triazole in 50 ml tetrahydrofuran. The mixture was refluxed and 0.85 g (0.005 mol) 3-(4-chlorophenyl)-2-propenenitrile in 30 ml tetrahydrofuran were added during, aperiod of 5.5 hours. Boiling was continued for 30 minutes and then 20 ml methanol were added at room temperature. Evaporation of the solvent and chromatography on silicagel with dichloromethane/methanol 99/1 gave 0.57 g (35%) 7-(4-chloro-phenyl)-2-furan-2-yl-[1,2,4]triazolo[1,5-a]pyridin-5-ylamine as pale crystals. MS m/e (%): 311 (M+H+, 100). The mixture was refluxed Evaporation of the solvent and chromatography on silicagel with dichloromethane/methanol 99/1

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

実験手順: The starting material may be prepared as follows: A solution of 25.8 g of ethyl (diethoxymethyl)phosphonite and 18.0 g of 4-chlorocinnamonitrile in 100 ml of ethanol is added to a stirred mixture of 1.2 g of sodium hydride (50% dispersion in oil) in 30 ml of ethanol at 0° C. under an atmosphere of nitrogen. The reaction mixture is allowed to warm to room temperature and stirred for 4 hours. 1 ml of glacial acetic acid is added and the mixture is concentrated under reduced pressure. The resulting crude product is dissolved in 50 ml of ethyl acetate, washed twice with 25 ml of water and the organic extract is dried over magnesium sulphate, and then concentrated under reduced pressure. The crude product is distilled under reduced pressure to give ethyl 1-(4-chlorophenyl)-2-cyanoethyl(diethoxymethyl)phosphinate, b.p. 180°-200° C./0.02 mbar, 31P=+37.9 and +37.8 ppm (CDCl3). The starting material may be prepared the mixture is concentrated under reduced pressure The resulting crude product is dissolved in 50 ml of ethyl acetate washed twice with 25 ml of water the organic extract is dried over magnesium sulphate concentrated under reduced pressure The crude product is distilled under reduced pressure

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

実験手順: The starting material may be prepared as follows: A solution of 25.8 g of ethyl (diethoxymethyl)phosphonite and 18.0 g of 4-chlorocinnamonitrile in 100 ml of ethanol is added to a stirred mixture of 1.2 g of sodium hydride (50% dispersion in oil) in 30 ml of ethanol at 0° C. under an atmosphere of nitrogen. The reaction mixture is allowed to warm to room temperature and stirred for 4 hours. 1 ml of glacial acetic acid is added and the mixture is concentrated under reduced pressure. The resulting crude product is dissolved in 50 ml of ethyl acetate, washed twice with 25 ml of water and the organic extract is dried over magnesium sulphate, and then concentrated under reduced pressure. The crude product is distilled under reduced pressure to give ethyl 1-(4-chlorophenyl)-2-cyanoethyl(diethoxymethyl)phosphinate, b.p. 180°-200° C./0.02 mbar, 31P=+37.9 and +37.8 ppm (CDCl3). The starting material may be prepared the mixture is concentrated under reduced pressure The resulting crude product is dissolved in 50 ml of ethyl acetate washed twice with 25 ml of water the organic extract is dried over magnesium sulphate concentrated under reduced pressure The crude product is distilled under reduced pressure

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

実験手順: A solution of 3-(4-chloro-phenyl)-acrylonitrile (1.63 g, 10 mmol) and hydroxyamine (0.74 ml, 12 mmol) in ethanol (10 ml) was stirred at room temperature overnight. The solvent was evaporated, and the residue was purified by column chromatography (EtOAc: Hexane=1:3) to give 1.0 g (51%) of 3-(4-chloro-phenyl)-N-hydroxy-acrylamidine. The solvent was evaporated the residue was purified by column chromatography (EtOAc: Hexane=1:3)

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

実験手順: A solution of 25.8 g of ethyl(diethoxymethyl)phosphonite and 18.0 g of 4-chlorocinnamonitrile in 100 ml of ethanol is added to a stirred mixture of 1.2 g of sodium hydride (50% dispersion in oil) in 30 ml of ethanol at 0° C. under an atmosphere of nitrogen. The reaction mixture is allowed to warm to room temperature and stirred for 4 hours. 1 ml of glacial acetic acid is added and the mixture is concentrated under reduced pressure. The resulting crude product is dissolved in 50 ml of ethyl acetate, washed twice with 25 ml of water and the organic extract is dried over magnesium sulphate, and then concentrated under reduced pressure. The crude product is distilled under reduced pressure to give ethyl 1-(4-chlorophenyl)-2-cyanoethyl(diethoxymethyl)phosphinate, b.p. 180°-200° C./0.02 mbar, 31P=+37.9 and +37.8 ppm (CDCl3). the mixture is concentrated under reduced pressure The resulting crude product is dissolved in 50 ml of ethyl acetate washed twice with 25 ml of water the organic extract is dried over magnesium sulphate concentrated under reduced pressure The crude product is distilled under reduced pressure

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

実験手順: Hydroxylamine hydrochloride (13.0 g.) was dissolved in dry methanol (100 ml.) and neutralised to phenolphthalein with a solution of sodium (6 g.) in methanol (60 ml.). The precipitated sodium chloride was filtered off and the filtrate was refluxed with p-chlorocinnamonitrile (9.4 g.) for 2 hrs. Thin layer chromatography showed the reaction to be complete after this time. The reaction mixture was evaporated to dryness in vacuo and the residue was crystallised from ethanol to produce colourless of crystals of p-chlorocinnamamidoxime, 4.16 g. (37%) m.p. 102°-4° λmax (EtOH), 273 nm., ε17500, τ(CDCl3) 2.68 (aromatic), 3.00 (OH), 5.16 (NH2), 3.13 (doublet, J=16 c./sec.), 3.58 (doublet, J=16 c./sec.). p-Chlorocinnamonitrile was prepared by NH2OH treatment and dehydrations of p-chlorocinnamaldehyde (J. Chem. Soc., 1965, 1564). p-Chlorocinnamaldehyde was prepared from p-chloro benzaldehyde and CH3CHO cf. G. Cigarella, E. Occelli, and E. Testa, (J. Med. Chem., 1965, 8, 326).

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

実験手順: The starting material may be prepared as follows: A solution of 25.8 g of ethyl(diethoxymethyl)phosphonite and 18.0 g of 4-chlorocinnamonitrile in 100 ml of ethanol is added to a stirred mixture of 1.2 g of sodium hydride (50% dispersion in oil) in 30 ml of ethanol at 0° C. under an atmosphere of nitrogen. The reaction mixture is allowed to warm to room temperature and stirred for 4 hours. 1 ml of glacial acetic acid is added and the mixture is concentrated under reduced pressure. The resulting crude product is dissolved in 50 ml of ethyl acetate, washed twice with 25 ml of water and the organic extract is dried over magnesium sulphate, and then concentrated under reduced pressure. The crude product is distilled under reduced pressure to give ethyl 1-(4-chlorophenyl)-2-cyanoethyl(diethoxymethyl)phosphinate, b.p. 180°-200° C./0.02 mbar, 31P=+37.9 and +37.8 ppm (CDCl3). The starting material may be prepared the mixture is concentrated under reduced pressure The resulting crude product is dissolved in 50 ml of ethyl acetate washed twice with 25 ml of water the organic extract is dried over magnesium sulphate concentrated under reduced pressure The crude product is distilled under reduced pressure

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

実験手順: 0.7 g (0.015 mol) sodiumhydride (55%) were added to a solution of 1.50 g (0.005 mol) 3-benzenesulfonylmethyl-5-furan-2-yl-1H-[1,2,4]triazole in 50 ml tetrahydrofuran. The mixture was refluxed and 0.85 g (0.005 mol) 3-(4-chlorophenyl)-2-propenenitrile in 30 ml tetrahydrofuran were added during, aperiod of 5.5 hours. Boiling was continued for 30 minutes and then 20 ml methanol were added at room temperature. Evaporation of the solvent and chromatography on silicagel with dichloromethane/methanol 99/1 gave 0.57 g (35%) 7-(4-chloro-phenyl)-2-furan-2-yl-[1,2,4]triazolo[1,5-a]pyridin-5-ylamine as pale crystals. MS m/e (%): 311 (M+H+, 100). The mixture was refluxed Evaporation of the solvent and chromatography on silicagel with dichloromethane/methanol 99/1

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

実験手順: A solution of 25.8 g of ethyl (diethoxymethyl)phosphonite and 18.0 g of 4-chlorocinnamonitrile in 100 ml of ethanol is added to a stirred mixture of 1.2 g of sodium hydride (50% dispersion in oil) in 30 ml of ethanol at 0° C. under an atmosphere of nitrogen. The reaction mixture is allowed to warm to room temperature and stirred for 4 hours. 1 ml of glacial acetic acid is added and the mixture is concentrated under reduced pressure. The resulting crude product is dissolved in 50 ml of ethyl acetate, washed twice with 25 ml of water and the organic extract is dried over magnesium sulphate, and then concentrated under reduced pressure. The crude product is distilled under reduced pressure to give ethyl 1-(4-chlorophenyl)-2-cyanoethyl(diethoxymethyl)phosphinate, b.p. 180°-200° C./0.02 mbar, 31P=+37.9 and +37.8 ppm (CDCl3). the mixture is concentrated under reduced pressure The resulting crude product is dissolved in 50 ml of ethyl acetate washed twice with 25 ml of water the organic extract is dried over magnesium sulphate concentrated under reduced pressure The crude product is distilled under reduced pressure

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

実験手順: A solution of 25.8 g of ethyl (diethoxymethyl)phosphonite and 18.0 g of 4-chlorocinnamonitrile in 100 ml of ethanol is added to a stirred mixture of 1.2 g of sodium hydride (50% dispersion in oil) in 30 ml of ethanol at 0° C. under an atmosphere of nitrogen. The reaction mixture is allowed to warm to room temperature and stirred for 4 hours. 1 ml of glacial acetic acid is added and the mixture is concentrated under reduced pressure. The resulting crude product is dissolved in 50 ml of ethyl acetate, washed twice with 25 ml of water and the organic extract is dried over magnesium sulphate, and then concentrated under reduced pressure. The crude product is distilled under reduced pressure to give ethyl 1-(4-chlorophenyl)-2-cyanoethyl(diethoxymethyl)phosphinate, b.p. 180°-200° C./0.02 mbar, 31P=+37.9 and +37.8 ppm (CDCl3). the mixture is concentrated under reduced pressure The resulting crude product is dissolved in 50 ml of ethyl acetate washed twice with 25 ml of water the organic extract is dried over magnesium sulphate concentrated under reduced pressure The crude product is distilled under reduced pressure