2-ethylhexyl 2-cyanoacetate

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: 36.3 g (0.3 mol) of p-aminobenzaldehyde are suspended in 450 ml of isopropanol. A mixture of 59.1 g (0.3 mol) of 2-ethylhexyl cyanoacetate and of catalyst (0.375 ml of diethylamine and 1.125 ml of acetic acid) is introduced therein. The mixture is refluxed for 5 hours. The same amount of catalyst is added again and refluxing is continued for a further 4 hours. The insoluble materials are removed by hot filtration and the mixture is concentrated to a volume of 300 ml and left to crystalize. After filtration and drying, 59.6 g (66% yield) of an orange-coloured powder are obtained, and are used without further purification for the following step. The mixture is refluxed for 5 hours The same amount of catalyst is added again refluxing The insoluble materials are removed by hot filtration the mixture is concentrated to a volume of 300 ml left to crystalize After filtration drying

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

実験手順: A mixture of 35 g (0.18 mol) of 2-ethylhexyl cyanoacetate and 30 g (0.18 mol) of 4-acetamidobenzaldehyde in 300 ml of isopropanol is refluxed for 3 hours. The reaction mixture is then allowed to cool and is crystallized. The crystals formed are separated out by filtration and are recrystallized from a minimum amount of isopropanol. After filtration and drying, 33.3 g (54% yield) of 2-ethylhexyl 3-(4-acetylaminophenyl)-2-cyanoacrylate are obtained in the form of a pale yellow powder. is refluxed for 3 hours to cool is crystallized The crystals formed are separated out by filtration are recrystallized from a minimum amount of isopropanol After filtration drying

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Into a 500 ml four-neck round-bottom flask, equipped with a mechanical stirrer, a thermometer and a condenser is charged with 62.2 g (0.32 mol) of 2-Ethylhexyl cyanoacetate (EHCA) and 81.0 g (0.45 mol) of Benzophenone (BP) (molar ratio EHCA:BP=0.71:1) and 27.7 g (0.36 mol) of ammonium acetate and 81.0 g (1.1 mol) of propionic acid and 81.0 g of heptane. The mixture is heated under stirring. When the temperature reach 110° C., a mixture of propionic acid, water, heptane is distilled off over a period of 5 hours at normal pressure. Heptane phase is returned back to the flask. Then the reactant is cooled to 90° C., and 100 ml of hot water is added to the reaction mixture. The mixture is kept at 85° C. for 10 minutes, and then transferred to a funnel for separation. To a flask equipped with a column 256.0 g of crude 2-ethylhexyl 2-cyano-3,3-diphenylacrylate solution is added. Rectification is carried out at 1 mbar. 2-Ethylhexyl 2-cyano-3,3-diphenylacrylate is distilled out at 210° C. (vapor). After distillation, light yellow 2-ethylhexyl 2-cyano-3,3-diphenylacrylate is obtained. Reaction yields are as indicated in table 1 and assume recycle of unreacted benzophenone and 2-EHCA. Into a 500 ml four-neck round-bottom flask, equipped with a mechanical stirrer The mixture is heated reach 110° C. is distilled off over a period of 5 hours at normal pressure 100 ml of hot water is added to the reaction mixture transferred to a funnel for separation To a flask equipped with a column 256.0 g of crude 2-ethylhexyl 2-cyano-3,3-diphenylacrylate solution is added 2-Ethylhexyl 2-cyano-3,3-diphenylacrylate is distilled out at 210° C. (vapor) After distillation

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a 1000 ml four neck flask fitted with mechanical agitator, thermometer, Dean and Stark apparatus and water condenser, add 237.5 g (2.23 mol on pure substance) 80 wt.-% cyanoacetic acid in water, 440 g (3.38 mol) 2-ethylhexanol and 1.2 g (6.3 mmol) p-toluenesulfonic acid monohydrate. Afterwards, the mixture is heated to reflux (110° C.) under atmospheric pressure for 1 hour and the water (both initial and formed) is azeotropically distilled out using a Dean and Stark apparatus returning the upper organic layer to the reactor. After 1 hour and at a temperature of 130° C. gradually a vacuum of 400 mbar is applied using a water respirator. The azeotropic distillation is maintained for further 6 hours while gradually increasing the vacuum from 400 mbar to 30 mbar in order to maintain a temperature of 130° C. until no further water is removed. After releasing the vacuum the reaction mixture is cooled to 90° C. After the addition of about 100 ml water (pre heated to 90° C.), the mixture is stirred at 85-90° C. for 10 minutes before separation of the phases. The upper organic layer is transferred to a 1000 ml four neck flask fitted with mechanical agitator, thermometer, packed column (ID=30 mm, H=1200 mm, packing metal raschid rings D=7 mm), water condenser and distillate flasks. Excess 2-Ethylhexanol is distilled out at 130-140° C. under a vacuum of 10-30 mbar. When complete increase the vacuum to 1.5 mbar and distilled out 2-ethylhexyl cyanoacetate at 130-140° C. 2-Ethylhexyl cyanoacetate is obtained as a colourless liquid. The reaction yield is 92% (based on cyanoacetic acid). Afterwards, the mixture is heated is azeotropically distilled out at a temperature of 130° C. The azeotropic distillation is maintained for further 6 hours while gradually increasing the vacuum from 400 mbar to 30 mbar in order to maintain a temperature of 130° C. until no further water is removed is cooled to 90° C After the addition of about 100 ml water (pre heated to 90° C.) fitted with mechanical agitator Excess 2-Ethylhexanol is distilled out at 130-140° C. under a vacuum of 10-30 mbar When complete increase the vacuum to 1.5 mbar distilled out 2-ethylhexyl cyanoacetate at 130-140° C

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a 1000 ml four neck flask fitted with mechanical agitator, thermometer, Dean and Stark apparatus and water condenser, add 237.5 g (2.23 mol on pure substance) 80 wt.-% cyanoacetic acid in water, 440 g (3.38 mol) 2-ethylhexanol and 1.2 g (6.3 mmol) p-toluenesulfonic acid monohydrate. Afterwards, the mixture is heated to reflux (110° C.) under atmospheric pressure for 1 hour and the water (both initial and formed) is azeotropically distilled out using a Dean and Stark apparatus returning the upper organic layer to the reactor. After 1 hour and at a temperature of 130° C. gradually a vacuum of 400 mbar is applied using a water respirator. The azeotropic distillation is maintained for further 6 hours while gradually increasing the vacuum from 400 mbar to 30 mbar in order to maintain a temperature of 130° C. until no further water is removed. After releasing the vacuum the reaction mixture is cooled to 90° C. After the addition of about 100 ml water (pre heated to 90° C.), the mixture is stirred at 85-90° C. for 10 minutes before separation of the phases. The upper organic layer is transferred to a 1000 ml four neck flask fitted with mechanical agitator, thermometer, packed column (ID=30 mm, H=1200 mm, packing metal raschid rings D=7 mm), water condenser and distillate flasks. Excess 2-Ethylhexanol is distilled out at 130-140° C. under a vacuum of 10-30 mbar. When complete increase the vacuum to 1.5 mbar and distilled out 2-ethylhexyl cyanoacetate at 130-140° C. 2-Ethylhexyl cyanoacetate is obtained as a colourless liquid. The reaction yield is 92% (based on cyanoacetic acid). Afterwards, the mixture is heated is azeotropically distilled out at a temperature of 130° C. The azeotropic distillation is maintained for further 6 hours while gradually increasing the vacuum from 400 mbar to 30 mbar in order to maintain a temperature of 130° C. until no further water is removed is cooled to 90° C After the addition of about 100 ml water (pre heated to 90° C.) fitted with mechanical agitator Excess 2-Ethylhexanol is distilled out at 130-140° C. under a vacuum of 10-30 mbar When complete increase the vacuum to 1.5 mbar distilled out 2-ethylhexyl cyanoacetate at 130-140° C

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

実験手順: 36.3 g (0.3 mol) of p-aminobenzaldehyde are suspended in 450 ml of isopropanol. A mixture of 59.1 g (0.3 mol) of 2-ethylhexyl cyanoacetate and of catalyst (0.375 ml of diethylamine and 1.125 ml of acetic acid) is introduced therein. The mixture is refluxed for 5 hours. The same amount of catalyst is added again and refluxing is continued for a further 4 hours. The insoluble materials are removed by hot filtration and the mixture is concentrated to a volume of 300 ml and left to crystalize. After filtration and drying, 59.6 g (66% yield) of an orange-coloured powder are obtained, and are used without further purification for the following step. The mixture is refluxed for 5 hours The same amount of catalyst is added again refluxing The insoluble materials are removed by hot filtration the mixture is concentrated to a volume of 300 ml left to crystalize After filtration drying

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

実験手順: 36.3 g (0.3 mol) of p-aminobenzaldehyde are suspended in 450 ml of isopropanol. A mixture of 59.1 g (0.3 mol) of 2-ethylhexyl cyanoacetate and of catalyst (0.375 ml of diethylamine and 1.125 ml of acetic acid) is introduced therein. The mixture is refluxed for 5 hours. The same amount of catalyst is added again and refluxing is continued for a further 4 hours. The insoluble materials are removed by hot filtration and the mixture is concentrated to a volume of 300 ml and left to crystalize. After filtration and drying, 59.6 g (66% yield) of an orange-coloured powder are obtained, and are used without further purification for the following step. The mixture is refluxed for 5 hours The same amount of catalyst is added again refluxing The insoluble materials are removed by hot filtration the mixture is concentrated to a volume of 300 ml left to crystalize After filtration drying

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

実験手順: A mixture of 35 g (0.18 mol) of 2-ethylhexyl cyanoacetate and 30 g (0.18 mol) of 4-acetamidobenzaldehyde in 300 ml of isopropanol is refluxed for 3 hours. The reaction mixture is then allowed to cool and is crystallized. The crystals formed are separated out by filtration and are recrystallized from a minimum amount of isopropanol. After filtration and drying, 33.3 g (54% yield) of 2-ethylhexyl 3-(4-acetylaminophenyl)-2-cyanoacrylate are obtained in the form of a pale yellow powder. is refluxed for 3 hours to cool is crystallized The crystals formed are separated out by filtration are recrystallized from a minimum amount of isopropanol After filtration drying

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

実験手順: 36.3 g (0.3 mol) of p-aminobenzaldehyde are suspended in 450 ml of isopropanol. A mixture of 59.1 g (0.3 mol) of 2-ethylhexyl cyanoacetate and of catalyst (0.375 ml of diethylamine and 1.125 ml of acetic acid) is introduced therein. The mixture is refluxed for 5 hours. The same amount of catalyst is added again and refluxing is continued for a further 4 hours. The insoluble materials are removed by hot filtration and the mixture is concentrated to a volume of 300 ml and left to crystalize. After filtration and drying, 59.6 g (66% yield) of an orange-coloured powder are obtained, and are used without further purification for the following step. The mixture is refluxed for 5 hours The same amount of catalyst is added again refluxing The insoluble materials are removed by hot filtration the mixture is concentrated to a volume of 300 ml left to crystalize After filtration drying