ethyl 2-bromo-2-(4-chlorophenyl)acetate

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of ethyl α-bromo-4-chlorophenylacetate (37.3 g), anhydrous potassium fluoride (9.7 g) and dry dimethylformamide (75 ml) was heated with stirring at a temperature of 140°-150° C. for a period of 6 hours. The reaction mixture was poured into water and the aqueous mixture extracted with methylene dichloride. The organic extract was washed with aqueous sodium carbonate, dried over anhydrous sodium sulfate and the solvent was removed by distillation under reduced pressure. The product was distilled using a spinning band column to give ethyl α-fluoro-4-chlorophenylacetate (7.5 g; 29%) b.p. 67° C. at 0.06 mm Hg. was heated the aqueous mixture extracted with methylene dichloride The organic extract was washed with aqueous sodium carbonate dried over anhydrous sodium sulfate the solvent was removed by distillation under reduced pressure The product was distilled

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4-chlorophenylacetic acid (34 g) and red phosphorus (1.5 g) was stirred under an atmosphere of nitrogen and dry bromine (20 g) was carefully added over a period of 30 minutes. The reaction mixture was heated to a temperature of 100° C. and dry bromine (32 g) was carefully added over a period of 45 minutes. The mixture was then heated under reflux for 3 hours and cooled. Ethyl alcohol (100 ml) was added to the reaction mixture and the mixture allowed to stand overnight. The ethanolic mixture was diluted with water and extracted with ethylene dichloride. The extract was washed with aqueous sodium carbonate, dried over anhydrous sodium sulfate and the solvent removed by distillation under reduced pressure. The product was distilled through a Fenske ring column to give ethyl α-bromo-4-chlorophenylacetate (33.4 g; 65%) b.p. 119° C. at 0.9 mm of Hg. was carefully added over a period of 45 minutes The mixture was then heated under reflux for 3 hours cooled extracted with ethylene dichloride The extract was washed with aqueous sodium carbonate dried over anhydrous sodium sulfate the solvent removed by distillation under reduced pressure The product was distilled through a Fenske ring column

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of ethyl α-bromo-4-chlorophenylacetate (37.3 g), anhydrous potassium fluoride (9.7 g) and dry dimethylformamide (75 ml) was heated with stirring at a temperature of 140°-150° C. for a period of 6 hours. The reaction mixture was poured into water and the aqueous mixture extracted with methylene dichloride. The organic extract was washed with aqueous sodium carbonate, dried over anhydrous sodium sulfate and the solvent was removed by distillation under reduced pressure. The product was distilled using a spinning band column to give ethyl α-fluoro-4-chlorophenylacetate (7.5 g; 29%) b.p. 67° C. at 0.06 mm Hg. was heated the aqueous mixture extracted with methylene dichloride The organic extract was washed with aqueous sodium carbonate dried over anhydrous sodium sulfate the solvent was removed by distillation under reduced pressure The product was distilled

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of ethyl α-bromo-4-chlorophenylacetate (37.3 g), anhydrous potassium fluoride (9.7 g) and dry dimethylformamide (75 ml) was heated with stirring at a temperature of 140°-150° C. for a period of 6 hours. The reaction mixture was poured into water and the aqueous mixture extracted with methylene dichloride. The organic extract was washed with aqueous sodium carbonate, dried over anhydrous sodium sulfate and the solvent was removed by distillation under reduced pressure. The product was distilled using a spinning band column to give ethyl α-fluoro-4-chlorophenylacetate (7.5 g; 29%) b.p. 67° C. at 0.06 mm Hg. was heated the aqueous mixture extracted with methylene dichloride The organic extract was washed with aqueous sodium carbonate dried over anhydrous sodium sulfate the solvent was removed by distillation under reduced pressure The product was distilled

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4-chlorophenylacetic acid (34 g) and red phosphorus (1.5 g) was stirred under an atmosphere of nitrogen and dry bromine (20 g) was carefully added over a period of 30 minutes. The reaction mixture was heated to a temperature of 100° C. and dry bromine (32 g) was carefully added over a periof of 45 minutes. The mixture was then heated under reflux for 3 hours and cooled. Ethyl alcohol (100 ml) was added to the reaction mixture and the mixture allowed to stand overnight. The ethanolic mixture was diluted with water and extracted with ethylene dichloride. The extract was washed with aqueous sodium carbonate, dried over anhydrous sodium sulfate and the solvent removed by distillation under reduced pressure. The product was distilled through a Fenske ring column to give ethyl α-bromo-4-chlorophenylacetate (33.4 g; 65%) b.p. 119° C. at 0.9 mm of Hg. was carefully added over a periof of 45 minutes The mixture was then heated under reflux for 3 hours cooled extracted with ethylene dichloride The extract was washed with aqueous sodium carbonate dried over anhydrous sodium sulfate the solvent removed by distillation under reduced pressure The product was distilled through a Fenske ring column

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of ethyl α-bromo-4-chlorophenylacetate (37.3 g), anhydrous potassium fluoride (9.7 g) and dry dimethylformamide (75 ml) was heated with stirring at a temperature of 140°-150° C. for a period of 6 hours. The reaction mixture was poured into water and the aqueous mixture extracted with methylene dichloride. The organic extract was washed with aqueous sodium carbonate, dried over anhydrous sodium sulfate and the solvent was removed by distillation under reduced pressure. The product was distilled using a spinning band column to give ethyl α-fluoro-4-chlorophenylacetate (7.5 g; 29%) b.p. 67° C. at 0.06 mm Hg. was heated the aqueous mixture extracted with methylene dichloride The organic extract was washed with aqueous sodium carbonate dried over anhydrous sodium sulfate the solvent was removed by distillation under reduced pressure The product was distilled

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 4-chlorophenylacetic acid (34 g) and red phosphorus (1.5 g) was stirred under an atmosphere of nitrogen and dry bromine (20 g) was carefully added over a period of 30 minutes. The reaction mixture was heated to a temperature of 100° C. and dry bromine (32 g) was carefully added over a period of 45 minutes. The mixture was then heated under reflux for 3 hours and cooled. Ethyl alcohol (100 ml) was added to the reaction mixture and the mixture allowed to stand overnight. The ethanolic mixture was diluted with water and extracted with ethylene dichloride. The extract was washed with aqueous sodium carbonate, dried over anhydrous sodium sulfate and the solvent removed by distillation under reduced pressure. The product was distilled through a Fenske ring column to give ethyl α-bromo-4-chlorophenylacetate (33.4 g; 65%) b.p. 119° C. at 0.9 mm of Hg. was carefully added over a period of 45 minutes The mixture was then heated under reflux for 3 hours cooled extracted with ethylene dichloride The extract was washed with aqueous sodium carbonate dried over anhydrous sodium sulfate the solvent removed by distillation under reduced pressure The product was distilled through a Fenske ring column

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl(4-chlorophenyl)[(4-hydroxyphenyl)sulfanyl]acetate was prepared according to the general method as outlined in example 1 (step 1), starting from ethyl bromo(4-chlorophenyl)acetate (16.5 g, 59.6 mmol) and 4-mercaptophenol (7.5 g, 59.6 mmol); 18.8 g white solid. mp: 63° C.; Yield 97%; MS: 321.3 (M−H)−

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: By the method of T. Naito, et al., Chem. Pharm. Bull. 16, 544 (1968), incorporated herein by reference, 50.0 g (0.18 mole) of ethyl alpha-bromo-(4-chlorophenyl)acetate, 110 ml of concentrated ammonium hydroxide solution, and ammonia gas in 125 ml of ethanol were reacted to produce 20.0 g of alpha-amino(4-chlorophenyl)acetamide hydrobromide (m.p. 273°-280° C. dec.).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: By the method of E. Schwenk and D. Papa, J. A. C. S. 70, 3626 (1948), incorporated herein by reference, 86.8 g (0.509 mole) of p-chlorophenylacetic acid was treated with 100 ml of thionyl chloride. Subsequent reaction with 83.2 g (0.52 mole) of bromine followed by 100 ml of ethanol produced 78.9 g of ethyl alphabromo-(4-chlorophenyl)acetate as an oil.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of ethyl α-bromo-4-chlorophenylacetate (37.3 g), anhydrous potassium fluoride (9.7 g) and dry dimethylformamide (75 ml) was heated with stirring at a temperature of 140°-150° C. for a period of 6 hours. The reaction mixture was poured into water and the aqueous mixture extracted with methylene dichloride. The organic extract was washed with aqueous sodium carbonate, dried over anhydrous sodium sulfate and the solvent was removed by distillation under reduced pressure. The product was distilled using a spinning band column to give ethyl α-fluoro-4-chlorophenylacetate (7.5 g; 29%) b.p. 67° C. at 0.06 mm Hg. was heated the aqueous mixture extracted with methylene dichloride The organic extract was washed with aqueous sodium carbonate dried over anhydrous sodium sulfate the solvent was removed by distillation under reduced pressure The product was distilled