Ethyl 2,4-dichlorobenzoate

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: A mixture of 27.6 g of ethyl 2,4-dichlorobenzoate and 20.81 g of ethyl 3-pyridylacetate at 20°-25° is treated portionwise with 10.59 g of sodium methoxide. The mixture is subsequently heated at 65°-70° and resulting readily volatile products are blown off with dry nitrogen. After 20 hours, the mixture is treated with 40 ml of concentrated hydrochloric acid and heated at reflux temperature for 18 hours. The mixture is washed with diethyl ether and the aqueous phase is made basic by adding concentrated ammonia and extracted with methylene chloride. The organic phase is concentrated and the crude product is chromatographed on silica gel with methylene chloride/methanol (98:2) to yield 2',4'-dichloro-2-(3-pyridyl)-acetophenone, which can be crystallized from diethyl ether/n-pentane and melts at 55°-56°. The mixture is subsequently heated at 65°-70° resulting readily volatile products heated at reflux temperature for 18 hours The mixture is washed with diethyl ether by adding concentrated ammonia extracted with methylene chloride The organic phase is concentrated the crude product is chromatographed on silica gel with methylene chloride/methanol (98:2)

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture containing ethyl 2,4-dichlorobenzoate (10.0 g), potassium carbonate (9.44 g), dimethylformamide (50 ml), and mercaptoacetic acid (3.8 ml) was allowed to react with heat at 80° C. for 4 hours. to react

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture containing ethyl 2,4-dichlorobenzoate (10.0 g), potassium carbonate (9.44 g), dimethylformamide (50 ml), and mercaptoacetic acid (3.8 ml) was allowed to react with heat at 80° C. for 4 hours. to react

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

実験手順: A mixture of 43.8 g of ethyl 2,4-dichloro-benzoate and 8.2 g of anhydrous acetonitrile is added dropwise to a suspension of 6.1 g of 80% strength sodium hydride in 100 ml of anhydrous tetrahydrofuran in the course of about 1 hour under reflux. The mixture is heated at the boiling point under reflux for a further hour and cooled to room temperature and 150 ml of ether are added. The precipitate is filtered off with suction and dissolved in 50 ml of ice-water and the solution is acidified to pH=6 with 10% strength hydrochloric acid. The precipitate is filtered off cold with suction, rinsed with ice-water and dried in vacuo at 40° C. 12 g of 2,4-dichlorobenzoylacetonitrile of melting point 96°-98° C. are obtained. under reflux The mixture is heated at the boiling point under reflux for a further hour The precipitate is filtered off with suction dissolved in 50 ml of ice-water The precipitate is filtered off cold with suction rinsed with ice-water dried in vacuo at 40° C

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

実験手順: A mixture of 27.6 g of ethyl 2,4-dichlorobenzoate and 20.81 g of ethyl 3-pyridylacetate at 20°-25° is treated portionwise with 10.59 g of sodium methoxide. The mixture is subsequently heated at 65°-70° and resulting readily volatile products are blown off with dry nitrogen. After 20 hours, the mixture is treated with 40 ml of concentrated hydrochloric acid and heated at reflux temperature for 18 hours. The mixture is washed with diethyl ether and the aqueous phase is made basic by adding concentrated ammonia and extracted with methylene chloride. The organic phase is concentrated and the crude product is chromatographed on silica gel with methylene chloride/methanol (98:2) to yield 2',4'-dichloro-2-(3-pyridyl)-acetophenone, which can be crystallized from diethyl ether/n-pentane and melts at 55°-56°. The mixture is subsequently heated at 65°-70° resulting readily volatile products heated at reflux temperature for 18 hours The mixture is washed with diethyl ether by adding concentrated ammonia extracted with methylene chloride The organic phase is concentrated the crude product is chromatographed on silica gel with methylene chloride/methanol (98:2)

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture containing ethyl 2,4-dichlorobenzoate (10.0 g), potassium carbonate (9.44 g), dimethylformamide (50 ml), and mercaptoacetic acid (3.8 ml) was allowed to react with heat at 80° C. for 4 hours. to react

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture containing ethyl 2,4-dichlorobenzoate (10.0 g), potassium carbonate (9.44 g), dimethylformamide (50 ml), and mercaptoacetic acid (3.8 ml) was allowed to react with heat at 80° C. for 4 hours. to react

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture containing ethyl 2,4-dichlorobenzoate (10.0 g), potassium carbonate (9.44 g), dimethylformamide (50 ml), and mercaptoacetic acid (3.8 ml) was allowed to react with heat at 80° C. for 4 hours. to react

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: A mixture of 43.8 g of ethyl 2,4-dichloro-benzoate and 8.2 g of anhydrous acetonitrile is added dropwise to a suspension of 6.1 g of 80% strength sodium hydride in 100 ml of anhydrous tetrahydrofuran in the course of about 1 hour under reflux. The mixture is heated at the boiling point under reflux for a further hour and cooled to room temperature and 150 ml of ether are added. The precipitate is filtered off with suction and dissolved in 50 ml of ice-water and the solution is acidified to pH=6 with 10% strength hydrochloric acid. The precipitate is filtered off cold with suction, rinsed with ice-water and dried in vacuo at 40° C. 12 g of 2,4-dichlorobenzoylacetonitrile of melting point 96°-98° C. are obtained. under reflux The mixture is heated at the boiling point under reflux for a further hour The precipitate is filtered off with suction dissolved in 50 ml of ice-water The precipitate is filtered off cold with suction rinsed with ice-water dried in vacuo at 40° C

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

実験手順: A mixture of 43.8 g of ethyl 2,4-dichloro-benzoate and 8.2 g of anhydrous acetonitrile is added dropwise to a suspension of 6.1 g of 80% strength sodium hydride in 100 ml of anhydrous tetrahydrofuran in the course of about 1 hour under reflux. The mixture is heated at the boiling point under reflux for a further hour and cooled to room temperature and 150 ml of ether are added. The precipitate is filtered off with suction and dissolved in 50 ml of ice-water and the solution is acidified to pH=6 with 10% strength hydrochloric acid. The precipitate is filtered off cold with suction, rinsed with ice-water and dried in vacuo at 40° C. 12 g of 2,4-dichlorobenzoylacetonitrile of melting point 96°-98° C. are obtained. under reflux The mixture is heated at the boiling point under reflux for a further hour The precipitate is filtered off with suction dissolved in 50 ml of ice-water The precipitate is filtered off cold with suction rinsed with ice-water dried in vacuo at 40° C