1-(3-fluoro-4-hydroxyphenyl)ethanone

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

Procedure: To a stirred solution of 1-(3-fluoro-4-hydroxyphenyl)-1-ethanone (2.0 g, 12.98 mmol) in dioxane (3 ml) was added a solution of bromine (2.09 g, 13.1 mmol) in dioxane (12 ml), and the mixture was stirred for 16 hours. The mixture was concentrated in vacuo to give title compound (3.02 g, 99% yield). The compound was used for next reaction without purification. The mixture was concentrated in vacuo

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

Procedure: To a stirred solution of 1-(3-fluoro-4-hydroxyphenyl)-1-ethanone (2.0 g, 12.98 mmol) in dioxane (3 ml) was added a solution of bromine (2.09 g, 13.1 mmol) in dioxane (12 ml), and the mixture was stirred for 16 hours. The mixture was concentrated in vacuo to give title compound (3.02 g, 99% yield). The compound was used for next reaction without purification. The mixture was concentrated in vacuo

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

Procedure: To a stirred solution of 1-(3-fluoro-4-hydroxyphenyl)-1-ethanone (2.0 g, 12.98 mmol) in dioxane (3 ml) was added a solution of bromine (2.09 g, 13.1 mmol) in dioxane (12 ml), and the mixture was stirred for 16 hours. The mixture was concentrated in vacuo to give title compound (3.02 g, 99% yield). The compound was used for next reaction without purification. The mixture was concentrated in vacuo

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

Procedure: To a stirred solution of 1-(3-fluoro-4-hydroxyphenyl)-1-ethanone (2.0 g, 12.98 mmol) in dioxane (3 ml) was added a solution of bromine (2.09 g, 13.1 mmol) in dioxane (12 ml), and the mixture was stirred for 16 hours. The mixture was concentrated in vacuo to give title compound (3.02 g, 99% yield). The compound was used for next reaction without purification. The mixture was concentrated in vacuo

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

Procedure: To a stirred solution of 1-(3-fluoro-4-hydroxyphenyl)-1-ethanone (2.0 g, 12.98 mmol) in dioxane (3 ml) was added a solution of bromine (2.09 g, 13.1 mmol) in dioxane (12 ml), and the mixture was stirred for 16 hours. The mixture was concentrated in vacuo to give title compound (3.02 g, 99% yield). The compound was used for next reaction without purification. The mixture was concentrated in vacuo

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

Procedure: A solution of 3′-fluoro-4′-hydroxyacetophenone (0.063 g, 0.411 mmol), O-(4-nitrobenzyl)hydroxylamine hydrochloride (0.100 g, 0.491 mmol) and pyridine (0.13 ml, 1.61 mmol) in ethanol (5 ml) was stirred at reflux under nitrogen for 5h and cooled to room temperature. The solution was concentrated to a pale yellow oil which was diluted with dichloromethane/water. The resultant mixture was extracted with dichloromethane (×3). The combined organic phases were washed with water and brine, dried over magnesium sulphate, filtered and concentrated to an off-white solid. The crude product was purified by column chromatography (SiO2), eluting with 8:2 petrol/ethyl acetate, to give a 3′-fluoro-4′-hydroxyacetophenone-O-4-nitrobenzyloxime (CP9-132) as light yellow solid (0.081 g, 65%), The solution was concentrated to a pale yellow oil which was diluted with dichloromethane/water The resultant mixture was extracted with dichloromethane (×3) The combined organic phases were washed with water and brine dried over magnesium sulphate filtered concentrated to an off-white solid The crude product was purified by column chromatography (SiO2) eluting with 8:2 petrol/ethyl acetate

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

Procedure: A solution of 3-fluoro-4-hydroxyacetophenone (0.061 g, 0.398 mmol), (benzo[c][1,2,5]oxadiazol-5-yl)methoxyamine hydrochloride (0.095 g, 0.470 mmol) and pyridine (0.13 ml, 1.61 mmol) in ethanol (5 ml) was stirred at reflux under nitrogen for 4 h and cooled to room temperature. The solution was concentrated to a pale yellow oil which was diluted with water. The resultant suspension was extracted with dichloromethane (×3). The combined organic phases were washed with water and brine, dried over magnesium sulphate, filtered and concentrated to an off-white solid. The crude product was purified by column chromatography (SiO2), eluting with 9:1 petrol/ethyl acetate, to give a pale beige solid which was further washed with petrol/dichloromethane to give 3′-fluoro-4′-hydroxyacetophenone-O-[(benzo[c][1,2,5]oxadiazol-5-yl)methyl]oxime (CP9-128) as a pale beige solid (0.098 g, 82%), m.p. 139-140°. at reflux under nitrogen for 4 h The solution was concentrated to a pale yellow oil which was diluted with water The resultant suspension was extracted with dichloromethane (×3) The combined organic phases were washed with water and brine dried over magnesium sulphate filtered concentrated to an off-white solid The crude product was purified by column chromatography (SiO2) eluting with 9:1 petrol/ethyl acetate to give a pale beige solid which was further washed with petrol/dichloromethane

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

Procedure: A solution of 3′-fluoro-4′-hydroxyacetophenone (0.063 g, 0.411 mmol), O-(4-nitrobenzyl)hydroxylamine hydrochloride (0.100 g, 0.491 mmol) and pyridine (0.13 ml, 1.61 mmol) in ethanol (5 ml) was stirred at reflux under nitrogen for 5h and cooled to room temperature. The solution was concentrated to a pale yellow oil which was diluted with dichloromethane/water. The resultant mixture was extracted with dichloromethane (×3). The combined organic phases were washed with water and brine, dried over magnesium sulphate, filtered and concentrated to an off-white solid. The crude product was purified by column chromatography (SiO2), eluting with 8:2 petrol/ethyl acetate, to give a 3′-fluoro-4′-hydroxyacetophenone-O-4-nitrobenzyloxime (CP9-132) as light yellow solid (0.081 g, 65%), The solution was concentrated to a pale yellow oil which was diluted with dichloromethane/water The resultant mixture was extracted with dichloromethane (×3) The combined organic phases were washed with water and brine dried over magnesium sulphate filtered concentrated to an off-white solid The crude product was purified by column chromatography (SiO2) eluting with 8:2 petrol/ethyl acetate

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

Procedure: A solution of 3-fluoro-4-hydroxyacetophenone (0.061 g, 0.398 mmol), (benzo[c][1,2,5]oxadiazol-5-yl)methoxyamine hydrochloride (0.095 g, 0.470 mmol) and pyridine (0.13 ml, 1.61 mmol) in ethanol (5 ml) was stirred at reflux under nitrogen for 4 h and cooled to room temperature. The solution was concentrated to a pale yellow oil which was diluted with water. The resultant suspension was extracted with dichloromethane (×3). The combined organic phases were washed with water and brine, dried over magnesium sulphate, filtered and concentrated to an off-white solid. The crude product was purified by column chromatography (SiO2), eluting with 9:1 petrol/ethyl acetate, to give a pale beige solid which was further washed with petrol/dichloromethane to give 3′-fluoro-4′-hydroxyacetophenone-O-[(benzo[c][1,2,5]oxadiazol-5-yl)methyl]oxime (CP9-128) as a pale beige solid (0.098 g, 82%), m.p. 139-140°. at reflux under nitrogen for 4 h The solution was concentrated to a pale yellow oil which was diluted with water The resultant suspension was extracted with dichloromethane (×3) The combined organic phases were washed with water and brine dried over magnesium sulphate filtered concentrated to an off-white solid The crude product was purified by column chromatography (SiO2) eluting with 9:1 petrol/ethyl acetate to give a pale beige solid which was further washed with petrol/dichloromethane

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

Procedure: After 1.70 g of sodium hydroxide was dissolved in 13 ml of water, 26 ml of ethanol and 5.10 g of 3-fluoro-4-hydroxyacetophenone were added and stirred under heating to form a homogeneous solution, and then 7.41 g of octylbromide was added thereto with stirring under heating. After the heating under reflux for 1 hour, 15 ml of acetone was added and then the heating was continued under reflux for 13 hours. After acetone and ethanol were distilled off, the reaction mixture was poured into 80 ml of water. After the extraction with ether was repeated three times, the organic layers were gathered, washed with water and dried on magnesium sulfate. After magnesium sulfate was filtered off, the filtrate was concentrated and dried under a reduced pressure to obtain 7.45 g of a slightly brown crystal. This crystal was recrystallized with a mixed solvent of methanol and water to obtain 5.07 g (yield: 58%) of a white crystal having a melting point of 39.6°-40.1° C. under heating to form a homogeneous solution with stirring under heating After the heating under reflux for 1 hour under reflux for 13 hours After acetone and ethanol were distilled off the reaction mixture was poured into 80 ml of water After the extraction with ether washed with water dried on magnesium sulfate After magnesium sulfate was filtered off the filtrate was concentrated dried under a reduced pressure to obtain 7.45 g of a slightly brown crystal This crystal was recrystallized with a mixed solvent of methanol and water

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

Procedure: After 1.70 g of sodium hydroxide was dissolved in 13 ml of water, 26 ml of ethanol and 5.10 g of 3-fluoro-4-hydroxyacetophenone were added and stirred under heating to form a homogeneous solution, and then 7.41 g of octylbromide was added thereto with stirring under heating. After the heating under reflux for 1 hour, 15 ml of acetone was added and then the heating was continued under reflux for 13 hours. After acetone and ethanol were distilled off, the reaction mixture was poured into 80 ml of water. After the extraction with ether was repeated three times, the organic layers were gathered, washed with water and dried on magnesium sulfate. After magnesium sulfate was filtered off, the filtrate was concentrated and dried under a reduced pressure to obtain 7.45 g of a slightly brown crystal. This crystal was recrystallized with a mixed solvent of methanol and water to obtain 5.07 g (yield: 58%) of a white crystal having a melting point of 39.6°-40.1° C. under heating to form a homogeneous solution with stirring under heating After the heating under reflux for 1 hour under reflux for 13 hours After acetone and ethanol were distilled off the reaction mixture was poured into 80 ml of water After the extraction with ether washed with water dried on magnesium sulfate After magnesium sulfate was filtered off the filtrate was concentrated dried under a reduced pressure to obtain 7.45 g of a slightly brown crystal This crystal was recrystallized with a mixed solvent of methanol and water

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

Procedure: After 1.70 g of sodium hydroxide was dissolved in 13 ml of water, 26 ml of ethanol and 5.10 g of 3-fluoro-4-hydroxyacetophenone were added and stirred under heating to form a homogeneous solution, and then 7.41 g of octylbromide was added thereto with stirring under heating. After the heating under reflux for 1 hour, 15 ml of acetone was added and then the heating was continued under reflux for 13 hours. After acetone and ethanol were distilled off, the reaction mixture was poured into 80 ml of water. After the extraction with ether was repeated three times, the organic layers were gathered, washed with water and dried on magnesium sulfate. After magnesium sulfate was filtered off, the filtrate was concentrated and dried under a reduced pressure to obtain 7.45 g of a slightly brown crystal. This crystal was recrystallized with a mixed solvent of methanol and water to obtain 5.07 g (yield: 58%) of a white crystal having a melting point of 39.6°-40.1° C. under heating to form a homogeneous solution with stirring under heating After the heating under reflux for 1 hour under reflux for 13 hours After acetone and ethanol were distilled off the reaction mixture was poured into 80 ml of water After the extraction with ether washed with water dried on magnesium sulfate After magnesium sulfate was filtered off the filtrate was concentrated dried under a reduced pressure to obtain 7.45 g of a slightly brown crystal This crystal was recrystallized with a mixed solvent of methanol and water