ethyl 2-chloropropanoate

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:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:77.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Sodium methyl sulfinate (103 g, 937 mmol) was combined with the ethyl 2-chloropropionate (109 g, 892 mmol) in ethanol (350 mL) in a 500 mL one neck round bottom flask. The reaction was heated to 77° C. for 20 h, and then allowed to cool to room temperature. Solids were removed by filtration through celite, and the filter pad was washed with ethanol. The combined filtrates were concentrated under reduced pressure. The crude product was suspended in diethyl ether (250 mL), and solids were removed by filtration. The filtrate was concentrated under reduced pressure to afford the title compound as a pale yellow oil (51 g, 73%). 1H NMR (400 MHz, CHLOROFORM-d) δ1.32 (t, J=7.05 Hz, 3H) 1.67 (d, J=7.47 Hz, 3H) 3.05 (s, 3H) 3.83-3.92 (m, 1H) 4.18-4.37 (m, 2H). to cool to room temperature Solids were removed by filtration through celite the filter pad was washed with ethanol The combined filtrates were concentrated under reduced pressure solids were removed by filtration The filtrate was concentrated under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of potassium t-butoxide (20 mmol) in DMF (20 mL) was added a mixture of 2-fluoro-nitrobenzene (10 mmol) and ethyl-2-chloropropionate (10 mmol) at 0° C. dropwise. After being stirred for 10 min at 0° C., the mixture was quenched by 1 N HCl solution, diluted with water and extracted with diethyl ether several times. The combined organic layers were washed with water and brine, dried over MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel using EtOAc:hexanes (1:10) as eluant to afford ethyl 2-(3-fluoro-4-nitrophenyl)propionate (1-1, SU-654). the mixture was quenched by 1 N HCl solution diluted with water extracted with diethyl ether several times The combined organic layers were washed with water and brine dried over MgSO4 concentrated in vacuo The residue was purified by flash column chromatography on silica gel

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

実験手順: A solution of 2-phenothiazinecarbonitrile (224.5 g) in dimethylformamide (1 liter) is introduced with stirring and in the course of 2 hours 30 minutes into a suspension of sodium hydride (24 g) in dimethylformamide (1 liter) at a temperature in the region of 25° C., an the mixture is left stirring for a further 1 hour 15 minutes until gaseous evolution has ceased. The fine suspension obtained is introduced with stirring in the course of 4 hours 30 minutes and at a temperature in the region of 25° C. into a solution of ethyl (2RS)-2-chloropropionate (255 cc) in dimethylformamide (1 liter) and stirring is continued for 16 hours. Ethanol (100 cc) is then poured into the reaction mixture and the whole is thereafter poured onto a mixture of ice (2 kg) in distilled water (4 liters); a gum precipitates and then crystallizes. The solid formed is drained, washed successively with distilled water (6×500 cc) and petroleum ether (2×500 cc) and dried in the air. Ethyl (2RS)-2-(2-cyano-10-phenothiazinyl)propionate (296.5 g) is thereby obtained in the form of khaki crystals, m.p. 117°-118° C., which are used without further treatment in the next step. an the mixture is left The fine suspension obtained is introduced stirring is continued for 16 hours a gum precipitates crystallizes The solid formed washed successively with distilled water (6×500 cc) and petroleum ether (2×500 cc) dried in the air

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Potassium carbonate (867 g, 6.29 mol) is added to a mixture of p-[(3,5-dichloro-2-pyridyl)oxy]phenol (1,609 g, 6.29 mol), 18-crown-6 (50 g, 0.19 mol) and tetrabutylammonium hydrogen sulfate (50 g, 0.15 mol) in dimethylformamide (20 L). Ethyl 2-chloropropionate (1,380 g, 10.10 mol) is then added and the reaction mixture is stirred for 2 days at 85° C., diluted with water and extracted with methylene chloride. The combined organic extracts are washed sequentially with water, 2% sodium hydroxide solution and water and concentrated in vacuo to give a residue. The residue is dissolved into a 1:1 toluene/heptane solution, washed with 2% sodium hydroxide solution and concentrated in vacuo to obtain the title product as a dark red-brown liquid (1,445 g) which is identified by 1HNMR spectral analysis. extracted with methylene chloride The combined organic extracts are washed sequentially with water, 2% sodium hydroxide solution and water concentrated in vacuo to give a residue washed with 2% sodium hydroxide solution concentrated in vacuo

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

実験手順: A solution of 73.5 g of 4-(4-trifluoromethylphenoxy)phenol and 49.2 g of ethyl α-chloropropionate and 100 g of potassium carbonate were added to 100 ml of methyl ethyl ketone, and the mixture was heated. With stirring, the reaction was performed for 10 hours at the reflux temperature (80° to 85° C.). Inorganic salts were separated from the reaction product by filtration. The filtrate was evaporated and dried. The resulting ester was extracted with chloroform, and washed with water. The chloroform was distilled off to afford 55 g of the final product (yield: 54%). The final product had a boiling point of 176° to 185° C./3 mmHg. the mixture was heated Inorganic salts were separated from the reaction product by filtration The filtrate was evaporated dried The resulting ester was extracted with chloroform washed with water The chloroform was distilled off

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

実験手順: A solution of 73.5 g of 4-(4-trifluoromethylphenoxy)phenol and 49.2 g of ethyl α-chloropropionate and 100 g of potassium carbonate were added to 100 ml of methyl ethyl ketone, and the mixture was heated. With stirring, the reaction was performed for 10 hours at the reflux temperature (80° to 85° C.). Inorganic salts were separated from the reaction product by filtration. The filtrate was evaporated and dried. The resulting ester was extracted with chloroform, and washed with water. The chloroform was distilled off to afford 55 g of the final product (yield: 54%). The final product had a boiling point of 176° to 185° C./3 mmHg. the mixture was heated Inorganic salts were separated from the reaction product by filtration The filtrate was evaporated dried The resulting ester was extracted with chloroform washed with water The chloroform was distilled off