ethyl 3-cyano-2-oxo-3-phenylpropanoate

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: To a solution of 6.6 g. (0.044 mol.) of p-chlorophenylacetonitrile and 20 ml. of dry glyme was added 6.2 g. (0.13 mol.) of sodium hydride (50% in oil). Ethyl 3-cyano-3-phenylpyruvate (9.55 g., 0.044 mol.) was added in portions at -10° and the reaction mixture was stirred at 25° for 12 hours. The mixture was diluted with 150 ml. of water, extracted with ether, acidified with 15 ml. of acetic acid and the solid was collected by filtration to yield 2-(p-chloro-phenyl)-5-phenyl-3,4-dioxoadiponitrile, m.p. 210° (dec.). The mixture was diluted with 150 ml of water, extracted with ether of acetic acid and the solid was collected by filtration

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

実験手順: To a solution of 6.6 g. (0.044 mol.) of p-chlorophenylacetonitrile and 20 ml. of dry glyme was added 6.2 g. (0.13 mol.) of sodium hydride (50% in oil). Ethyl 3-cyano-3-phenylpyruvate (9.55 g., 0.044 mol.) was added in portions at -10° and the reaction mixture was stirred at 25° for 12 hours. The mixture was diluted with 150 ml. of water, extracted with ether, acidified with 15 ml. of acetic acid and the solid was collected by filtration to yield 2-(p-chloro-phenyl)-5-phenyl-3,4-dioxoadiponitrile, m.p. 210° (dec.). The mixture was diluted with 150 ml of water, extracted with ether of acetic acid and the solid was collected by filtration

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

実験手順: A mixture of 117.1 g. (1.0 mol.) of phenylacetonitrile and 326 ml. (2.4 mol.) of ethyl oxalate was added to an ethanol solution of sodium ethoxide [prepared by dissolving 23.8 g. (1.08 g.-atom) of sodium in 500 ml. of absolute ethanol] and refluxed two hours. After cooling, diluting with 2500 ml. of water and extracting with ether, the solution was acidified with acetic acid. The solid was removed and washed with water to give ethyl 3-cyano-3-phenylpyruvate, m.p. 127°-129°. A mixture of 117.1 g refluxed two hours After cooling diluting with 2500 ml of water and extracting with ether The solid was removed washed with water

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

実験手順: A mixture of 117.1 g. (1.0 mol.) of phenylacetonitrile and 326 ml. (2.4 mol.) of ethyl oxalate was added to an ethanol solution of sodium ethoxide [prepared by dissolving 23.8 g. (1.08 g.-atom) of sodium in 500 ml. of absolute ethanol] and refluxed two hours. After cooling, diluting with 2500 ml. of water and extracting with ether, the solution was acidified with acetic acid. The solid was removed and washed with water to give ethyl 3-cyano-3-phenylpyruvate, m.p. 127°-129°. A mixture of 117.1 g refluxed two hours After cooling diluting with 2500 ml of water and extracting with ether The solid was removed washed with water

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

実験手順: Ethyl 3-cyano-3-phenylpyruvate (50.0 g., 0.23 mol.) and 41.0 g. (0.35 mol.) of phenylacetonitrile were added to an alcoholic solution of sodium ethoxide [prepared from 13.4 g. (0.58 g. -atom) of sodium and 360 ml. of absolute ethanol] and the resulting yellow solution was refluxed for 1.75 hours. The cooled solution was diluted with 700 ml. of water and acidified by slow addition of acetic acid. After further cooling in ice, the suspension was filtered and the solid was washed with water and dried to give 2,5-diphenyl-3,4-dioxoadiponitrile, m.p. 284°-286° (dec.). the resulting yellow solution was refluxed for 1.75 hours The cooled solution was diluted with 700 ml After further cooling in ice the suspension was filtered the solid was washed with water dried

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

実験手順: Ethyl 3-cyano-3-phenylpyruvate (50.0 g., 0.23 mol.) and 41.0 g. (0.35 mol.) of phenylacetonitrile were added to an alcoholic solution of sodium ethoxide [prepared from 13.4 g. (0.58 g. -atom) of sodium and 360 ml. of absolute ethanol] and the resulting yellow solution was refluxed for 1.75 hours. The cooled solution was diluted with 700 ml. of water and acidified by slow addition of acetic acid. After further cooling in ice, the suspension was filtered and the solid was washed with water and dried to give 2,5-diphenyl-3,4-dioxoadiponitrile, m.p. 284°-286° (dec.). the resulting yellow solution was refluxed for 1.75 hours The cooled solution was diluted with 700 ml After further cooling in ice the suspension was filtered the solid was washed with water dried

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

実験手順: A mixture of 117.1 g. (1.0 mol.) of phenylacetonitrile and 326 ml. (2.4 mol.) of ethyl oxalate was added to an ethanol solution of sodium ethoxide [prepared by dissolving 23.8 g. (1.08 g. -atom) of sodium in 500 ml. of absolute ethanol] and refluxed for two hours. After cooling, diluting with 2500 ml. of water and extracting with ether, the solution was acidified with acetic acid. The solid was removed by filtration and washed with water to give ethyl 3-cyano-3-phenylpyruvate, m.p. 127°-129°. A mixture of 117.1 g refluxed for two hours After cooling diluting with 2500 ml of water and extracting with ether The solid was removed by filtration washed with water

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

実験手順: A mixture of 117.1 g. (1.0 mol.) of phenylacetonitrile and 326 ml. (2.4 mol.) of ethyl oxalate was added to an ethanol solution of sodium ethoxide [prepared by dissolving 23.8 g. (1.08 g. -atom) of sodium in 500 ml. of absolute ethanol] and refluxed for two hours. After cooling, diluting with 2500 ml. of water and extracting with ether, the solution was acidified with acetic acid. The solid was removed by filtration and washed with water to give ethyl 3-cyano-3-phenylpyruvate, m.p. 127°-129°. A mixture of 117.1 g refluxed for two hours After cooling diluting with 2500 ml of water and extracting with ether The solid was removed by filtration washed with water

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

実験手順: As described in Example 1, ethyl 3-cyano-3-phenylpyruvate is reacted with p-methylthiophenylacetonitrile in an alcoholic solution of sodium ethoxide to give 2-(p-methylthiophenyl)-5-phenyl-3,4-dioxoadiponitrile. The latter is refluxed in a mixture of water, glacial acetic acid and concentrated sulfuric acid to give a mixture of 4- and 4'-methylthiopulvinic acid which is then refluxed in acetic anhydride to result in the formation of 4-methylthiopulvinic acid lactone.

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

実験手順: As described in Example 1, ethyl 3-cyano-3-phenylpyruvate is reacted with p-methylthiophenylacetonitrile in an alcoholic solution of sodium ethoxide to give 2-(p-methylthiophenyl)-5-phenyl-3,4-dioxoadiponitrile. The latter is refluxed in a mixture of water, glacial acetic acid and concentrated sulfuric acid to give a mixture of 4- and 4'-methylthiopulvinic acid which is then refluxed in acetic anhydride to result in the formation of 4-methylthiopulvinic acid lactone.

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

実験手順: To a solution of 6.6 g. (0.044 m.) of p-chlorophenylacetonitrile and 20 ml. of dry glyme is added 6.2 g. (0.13 m.) of sodium hydride (50% in oil). Ethyl 3-cyano-3-phenylpyruvate, 9.55 g. (0.044 m.) is added in portions at -10° C. and then the mixture is stirred at room temperature overnight. The reaction mixture is diluted with 150 ml. of water, extracted with ether, acidified with 15 ml. of acetic acid and the solid is filtered to yield 2-(p-chlorophenyl)-5-phenyl-3,4-dioxoadiponitrile, m.p. 210° C. (dec.). (0.044 m.) is added in portions at -10° C. The reaction mixture is diluted with 150 ml of water, extracted with ether of acetic acid and the solid is filtered