2-(4-chlorophenyl)-2,2-difluoroethanol

反応条件: temp:-60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A stirring solution of 7.0 grams (0.055 mole) of oxalyl chloride in 125 mL of methylene chloride is cooled to -60° C., and a solution of 9.5 grams (0.120 mole) of dimethyl sulfoxide in 25 mL of methylene chloride is added dropwise during a five minute period. Upon completion of addition, the reaction mixture is stirred at -60° C. for about 10 minutes, and then a solution of 9.6 grams (0.050 mole) of 2,2-difluoro-2-(4-chlorophenyl)ethanol in 25 mL of methylene chloride is added dropwise during a five minute period. Upon completion of addition, the reaction mixture is stirred for 15 minutes, and 25.5 grams (0.250 mole) of triethylamine is added while maintaining the reaction mixture temperature at -60° C. Upon completion of addition, the reaction mixture is allowed to warm to ambient temperature, and 150 mL of water is added. The mixture is stirred for 10 minutes, and the organic layer is separated. The aqueous layer is washed with 100 mL of methylene chloride. The methylene chloride wash and the organic layer are combined, and the combination is washed with 100 mL of water and then with 100 mL of an aqueous solution saturated with sodium chloride. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure, yielding difluoro-4-chlorophenylacetaldehyde. Upon completion of addition Upon completion of addition the reaction mixture is stirred for 15 minutes while maintaining the reaction mixture temperature at -60° C Upon completion of addition to warm to ambient temperature The mixture is stirred for 10 minutes the organic layer is separated The aqueous layer is washed with 100 mL of methylene chloride The methylene chloride wash the combination is washed with 100 mL of water The organic layer is dried with magnesium sulfate filtered The filtrate is concentrated under reduced pressure

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Lithium aluminum hydride, 2.4 grams (0.063 mole), is placed in a reaction vessel, and 200 mL of diethyl ether is added dropwise with stirring. To this is added dropwise a solution of 22.8 grams (0.097 mole) of ethyl 4-chlorophenyldifluoroacetate (prepared by methods taught by W. J. Middleton et al., J. Org. Chem., (1980), 45, 2883-2887) in 100 mL of diethyl ether, while maintaining the reaction mixture temperature at about 25° C. Upon completion of addition, the reaction mixture is stirred at ambient temperature for about 36 hours. The reaction is then quenched by the careful dropwise addition of an aqueous solution of 10% sodium hydroxide. The reaction mixture is slowly made acidic with aqueous 2N hydrochloric acid and then is diluted with 200 mL of water. The organic layer is separated, and the aqueous layer is washed with two 300 mL portions of diethyl ether. The organic layer and the diethyl ether washes are combined and washed with one 250 mL portion of an aqueous solution saturated with sodium chloride. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure, yielding 2,2-difluoro-2-(4-chlorophenyl)ethanol. Upon completion of addition the reaction mixture is stirred at ambient temperature for about 36 hours The reaction is then quenched by the careful dropwise addition of an aqueous solution of 10% sodium hydroxide is diluted with 200 mL of water The organic layer is separated the aqueous layer is washed with two 300 mL portions of diethyl ether washed with one 250 mL portion of an aqueous solution saturated with sodium chloride The organic layer is dried with magnesium sulfate filtered The filtrate is concentrated under reduced pressure

反応条件: temp:-60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A stirring solution of 7.0 grams (0.055 mole) of oxalyl chloride in 125 mL of methylene chloride is cooled to -60° C., and a solution of 9.5 grams (0.120 mole) of dimethyl sulfoxide in 25 mL of methylene chloride is added dropwise during a five minute period. Upon completion of addition, the reaction mixture is stirred at -60° C. for about 10 minutes, and then a solution of 9.6 grams (0.050 mole) of 2,2-difluoro-2-(4-chlorophenyl)ethanol in 25 mL of methylene chloride is added dropwise during a five minute period. Upon completion of addition, the reaction mixture is stirred for 15 minutes, and 25.5 grams (0.250 mole) of triethylamine is added while maintaining the reaction mixture temperature at -60° C. Upon completion of addition, the reaction mixture is allowed to warm to ambient temperature, and 150 mL of water is added. The mixture is stirred for 10 minutes, and the organic layer is separated. The aqueous layer is washed with 100 mL of methylene chloride. The methylene chloride wash and the organic layer are combined, and the combination is washed with 100 mL of water and then with 100 mL of an aqueous solution saturated with sodium chloride. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure, yielding difluoro-4-chlorophenylacetaldehyde. Upon completion of addition Upon completion of addition the reaction mixture is stirred for 15 minutes while maintaining the reaction mixture temperature at -60° C Upon completion of addition to warm to ambient temperature The mixture is stirred for 10 minutes the organic layer is separated The aqueous layer is washed with 100 mL of methylene chloride The methylene chloride wash the combination is washed with 100 mL of water The organic layer is dried with magnesium sulfate filtered The filtrate is concentrated under reduced pressure

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Lithium aluminum hydride, 2.4 grams (0.063 mole), is placed in a reaction vessel, and 200 mL of diethyl ether is added dropwise with stirring. To this is added dropwise a solution of 22.8 grams (0.097 mole) of ethyl 4-chlorophenyldifluoroacetate (prepared by methods taught by W. J. Middleton et al., J. Org. Chem., (1980), 45, 2883-2887) in 100 mL of diethyl ether, while maintaining the reaction mixture temperature at about 25° C. Upon completion of addition, the reaction mixture is stirred at ambient temperature for about 36 hours. The reaction is then quenched by the careful dropwise addition of an aqueous solution of 10% sodium hydroxide. The reaction mixture is slowly made acidic with aqueous 2N hydrochloric acid and then is diluted with 200 mL of water. The organic layer is separated, and the aqueous layer is washed with two 300 mL portions of diethyl ether. The organic layer and the diethyl ether washes are combined and washed with one 250 mL portion of an aqueous solution saturated with sodium chloride. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure, yielding 2,2-difluoro-2-(4-chlorophenyl)ethanol. Upon completion of addition the reaction mixture is stirred at ambient temperature for about 36 hours The reaction is then quenched by the careful dropwise addition of an aqueous solution of 10% sodium hydroxide is diluted with 200 mL of water The organic layer is separated the aqueous layer is washed with two 300 mL portions of diethyl ether washed with one 250 mL portion of an aqueous solution saturated with sodium chloride The organic layer is dried with magnesium sulfate filtered The filtrate is concentrated under reduced pressure

反応条件: temp:-60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A stirring solution of 7.0 grams (0.055 mole) of oxalyl chloride in 125 mL of methylene chloride is cooled to -60° C., and a solution of 9.5 grams (0.120 mole) of dimethyl sulfoxide in 25 mL of methylene chloride is added dropwise during a five minute period. Upon completion of addition, the reaction mixture is stirred at -60° C. for about 10 minutes, and then a solution of 9.6 grams (0.050 mole) of 2,2-difluoro-2-(4-chlorophenyl)ethanol in 25 mL of methylene chloride is added dropwise during a five minute period. Upon completion of addition, the reaction mixture is stirred for 15 minutes, and 25.5 grams (0.250 mole) of triethylamine is added while maintaining the reaction mixture temperature at -60° C. Upon completion of addition, the reaction mixture is allowed to warm to ambient temperature, and 150 mL of water is added. The mixture is stirred for 10 minutes, and the organic layer is separated. The aqueous layer is washed with 100 mL of methylene chloride. The methylene chloride wash and the organic layer are combined, and the combination is washed with 100 mL of water and then with 100 mL of an aqueous solution saturated with sodium chloride. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure, yielding difluoro-4-chlorophenylacetaldehyde. Upon completion of addition Upon completion of addition the reaction mixture is stirred for 15 minutes while maintaining the reaction mixture temperature at -60° C Upon completion of addition to warm to ambient temperature The mixture is stirred for 10 minutes the organic layer is separated The aqueous layer is washed with 100 mL of methylene chloride The methylene chloride wash the combination is washed with 100 mL of water The organic layer is dried with magnesium sulfate filtered The filtrate is concentrated under reduced pressure

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Lithium aluminum hydride, 2.4 grams (0.063 mole), is placed in a reaction vessel, and 200 mL of diethyl ether is added dropwise with stirring. To this is added dropwise a solution of 22.8 grams (0.097 mole) of ethyl 4-chlorophenyldifluoroacetate (prepared by methods taught by W. J. Middleton et al., J. Org. Chem., (1980), 45, 2883-2887) in 100 mL of diethyl ether, while maintaining the reaction mixture temperature at about 25° C. Upon completion of addition, the reaction mixture is stirred at ambient temperature for about 36 hours. The reaction is then quenched by the careful dropwise addition of an aqueous solution of 10% sodium hydroxide. The reaction mixture is slowly made acidic with aqueous 2N hydrochloric acid and then is diluted with 200 mL of water. The organic layer is separated, and the aqueous layer is washed with two 300 mL portions of diethyl ether. The organic layer and the diethyl ether washes are combined and washed with one 250 mL portion of an aqueous solution saturated with sodium chloride. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure, yielding 2,2-difluoro-2-(4-chlorophenyl)ethanol. Upon completion of addition the reaction mixture is stirred at ambient temperature for about 36 hours The reaction is then quenched by the careful dropwise addition of an aqueous solution of 10% sodium hydroxide is diluted with 200 mL of water The organic layer is separated the aqueous layer is washed with two 300 mL portions of diethyl ether washed with one 250 mL portion of an aqueous solution saturated with sodium chloride The organic layer is dried with magnesium sulfate filtered The filtrate is concentrated under reduced pressure

反応条件: temp:-60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A stirring solution of 7.0 grams (0.055 mole) of oxalyl chloride in 125 mL of methylene chloride is cooled to -60° C., and a solution of 9.5 grams (0.120 mole) of dimethyl sulfoxide in 25 mL of methylene chloride is added dropwise during a five minute period. Upon completion of addition, the reaction mixture is stirred at -60° C. for about 10 minutes, and then a solution of 9.6 grams (0.050 mole) of 2,2-difluoro-2-(4-chlorophenyl)ethanol in 25 mL of methylene chloride is added dropwise during a five minute period. Upon completion of addition, the reaction mixture is stirred for 15 minutes, and 25.5 grams (0.250 mole) of triethylamine is added while maintaining the reaction mixture temperature at -60° C. Upon completion of addition, the reaction mixture is allowed to warm to ambient temperature, and 150 mL of water is added. The mixture is stirred for 10 minutes, and the organic layer is separated. The aqueous layer is washed with 100 mL of methylene chloride. The methylene chloride wash and the organic layer are combined, and the combination is washed with 100 mL of water and then with 100 mL of an aqueous solution saturated with sodium chloride. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure, yielding difluoro-4-chlorophenylacetaldehyde. Upon completion of addition Upon completion of addition the reaction mixture is stirred for 15 minutes while maintaining the reaction mixture temperature at -60° C Upon completion of addition to warm to ambient temperature The mixture is stirred for 10 minutes the organic layer is separated The aqueous layer is washed with 100 mL of methylene chloride The methylene chloride wash the combination is washed with 100 mL of water The organic layer is dried with magnesium sulfate filtered The filtrate is concentrated under reduced pressure

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Lithium aluminum hydride, 2.4 grams (0.063 mole), is placed in a reaction vessel, and 200 mL of diethyl ether is added dropwise with stirring. To this is added dropwise a solution of 22.8 grams (0.097 mole) of ethyl 4-chlorophenyldifluoroacetate (prepared by methods taught by W. J. Middleton et al., J. Org. Chem., (1980), 45, 2883-2887) in 100 mL of diethyl ether, while maintaining the reaction mixture temperature at about 25° C. Upon completion of addition, the reaction mixture is stirred at ambient temperature for about 36 hours. The reaction is then quenched by the careful dropwise addition of an aqueous solution of 10% sodium hydroxide. The reaction mixture is slowly made acidic with aqueous 2N hydrochloric acid and then is diluted with 200 mL of water. The organic layer is separated, and the aqueous layer is washed with two 300 mL portions of diethyl ether. The organic layer and the diethyl ether washes are combined and washed with one 250 mL portion of an aqueous solution saturated with sodium chloride. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure, yielding 2,2-difluoro-2-(4-chlorophenyl)ethanol. Upon completion of addition the reaction mixture is stirred at ambient temperature for about 36 hours The reaction is then quenched by the careful dropwise addition of an aqueous solution of 10% sodium hydroxide is diluted with 200 mL of water The organic layer is separated the aqueous layer is washed with two 300 mL portions of diethyl ether washed with one 250 mL portion of an aqueous solution saturated with sodium chloride The organic layer is dried with magnesium sulfate filtered The filtrate is concentrated under reduced pressure