2-(dimethoxymethylidene)propanedinitrile

反応条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 4.2 g of 3-hydrazino-2-hydroxy-6-phenylhexane are are dissolved in 20 ml of methanol, and 1.38 ml of triethylamine are added. Then, 1.38 g of 1,1-dimethoxy-2,2-dicyano-ethylene are added. The reaction solution is stirred for 2 hours at approx. 20° C. For work-up, the mixture is diluted with citric acid solution and ethyl acetate and extracted three times with ethyl acetate. The combined ethyl acetate phases are dried with magnesium sulphate and evaporated in vacuo. The evaporation residue is chromatographed on silica gel (Merck Si 60 0.04-0.063 mm) with a cyclohexane/ethyl acetate mixture in a ratio of 4:1 to 1:1. This gives a fraction which, after evaporation in vacuo, affords 0.959 g (=30.5% of theory) of 5-amino-4-cyano-3-methoxy-1-[2-hydroxy-6-phenyl-hex-3-yl]-pyrazole as diastereomer mixture. extracted three times with ethyl acetate The combined ethyl acetate phases are dried with magnesium sulphate evaporated in vacuo The evaporation residue is chromatographed on silica gel (Merck Si 60 0.04-0.063 mm) with a cyclohexane/ethyl acetate mixture in a ratio of 4:1 to 1:1 This gives a fraction which after evaporation in vacuo

反応条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 4.2 g of 3-hydrazino-2-hydroxy-6-phenylhexane are are dissolved in 20 ml of methanol, and 1.38 ml of triethylamine are added. Then, 1.38 g of 1,1-dimethoxy-2,2-dicyano-ethylene are added. The reaction solution is stirred for 2 hours at approx. 20° C. For work-up, the mixture is diluted with citric acid solution and ethyl acetate and extracted three times with ethyl acetate. The combined ethyl acetate phases are dried with magnesium sulphate and evaporated in vacuo. The evaporation residue is chromatographed on silica gel (Merck Si 60 0.04-0.063 mm) with a cyclohexane/ethyl acetate mixture in a ratio of 4:1 to 1:1. This gives a fraction which, after evaporation in vacuo, affords 0.959 g (=30.5% of theory) of 5-amino-4-cyano-3-methoxy-1-[2-hydroxy-6-phenyl-hex-3-yl]-pyrazole as diastereomer mixture. extracted three times with ethyl acetate The combined ethyl acetate phases are dried with magnesium sulphate evaporated in vacuo The evaporation residue is chromatographed on silica gel (Merck Si 60 0.04-0.063 mm) with a cyclohexane/ethyl acetate mixture in a ratio of 4:1 to 1:1 This gives a fraction which after evaporation in vacuo

反応条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 3.6 g of 2-hydrazino-5-phenylpentane are dissolved in 40 ml of methanol, and 2.8 ml of triethylamine are added. Then, 2.8 g of 1,1-dimethoxy-2,2-dicyanoethylene are added at approx. 0° C. The reaction solution is warmed to approx. 20° C. and stirred for 1.5 hours at approx. 20° C. For work-up, the mixture is diluted with water, acidified with citric acid and extracted twice with dichloromethane. The combined dichloromethane phases are dried with magnesium sulphate and evaporated in vacuo. This gives 5.1 g of a yellow oil, which crystallizes slowly. The oil is chromatographed on silica gel (Merck Si 60 0.04-0.063 mm) with a petroleum ether/ethyl acetate mixture in a ratio of 5:1 to 1:1. This gives a fraction which, after evaporation in vacuo, affords 4.6 g (=80.9% of theory) of 5-amino-4-cyano-3-methoxy-1-[(5-phenyl)-pent-2-yl]-pyrazole. extracted twice with dichloromethane The combined dichloromethane phases are dried with magnesium sulphate evaporated in vacuo This gives 5.1 g of a yellow oil, which crystallizes slowly The oil is chromatographed on silica gel (Merck Si 60 0.04-0.063 mm) with a petroleum ether/ethyl acetate mixture in a ratio of 5:1 to 1:1 This gives a fraction which after evaporation in vacuo

反応条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 4.2 g of 3-hydrazino-2-hydroxy-6-phenylhexane are are dissolved in 20 ml of methanol, and 1.38 ml of triethylamine are added. Then, 1.38 g of 1,1-dimethoxy-2,2-dicyano-ethylene are added. The reaction solution is stirred for 2 hours at approx. 20° C. For work-up, the mixture is diluted with citric acid solution and ethyl acetate and extracted three times with ethyl acetate. The combined ethyl acetate phases are dried with magnesium sulphate and evaporated in vacuo. The evaporation residue is chromatographed on silica gel (Merck Si 60 0.04-0.063 mm) with a cyclohexane/ethyl acetate mixture in a ratio of 4:1 to 1:1. This gives a fraction which, after evaporation in vacuo, affords 0.959 g (=30.5% of theory) of 5-amino-4-cyano-3-methoxy-1-[2-hydroxy-6-phenyl-hex-3-yl]-pyrazole as diastereomer mixture. extracted three times with ethyl acetate The combined ethyl acetate phases are dried with magnesium sulphate evaporated in vacuo The evaporation residue is chromatographed on silica gel (Merck Si 60 0.04-0.063 mm) with a cyclohexane/ethyl acetate mixture in a ratio of 4:1 to 1:1 This gives a fraction which after evaporation in vacuo

反応条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 3.6 g of 2-hydrazino-5-phenylpentane are dissolved in 40 ml of methanol, and 2.8 ml of triethylamine are added. Then, 2.8 g of 1,1-dimethoxy-2,2-dicyanoethylene are added at approx. 0° C. The reaction solution is warmed to approx. 20° C. and stirred for 1.5 hours at approx. 20° C. For work-up, the mixture is diluted with water, acidified with citric acid and extracted twice with dichloromethane. The combined dichloromethane phases are dried with magnesium sulphate and evaporated in vacuo. This gives 5.1 g of a yellow oil, which crystallizes slowly. The oil is chromatographed on silica gel (Merck Si 60 0.04-0.063 mm) with a petroleum ether/ethyl acetate mixture in a ratio of 5:1 to 1:1. This gives a fraction which, after evaporation in vacuo, affords 4.6 g (=80.9% of theory) of 5-amino-4-cyano-3-methoxy-1-[(5-phenyl)-pent-2-yl]-pyrazole. extracted twice with dichloromethane The combined dichloromethane phases are dried with magnesium sulphate evaporated in vacuo This gives 5.1 g of a yellow oil, which crystallizes slowly The oil is chromatographed on silica gel (Merck Si 60 0.04-0.063 mm) with a petroleum ether/ethyl acetate mixture in a ratio of 5:1 to 1:1 This gives a fraction which after evaporation in vacuo