4-(ethylamino)phenol

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

実験手順: To a suspension of (4-hydroxy-phenyl)-ethylamine (3.14 g, 22.2 mmol) and Rhodanine (2.96 g, 22.2 mmol) in ethanol (314 mL) was added DIPEA (4.76 mL, 26.64 mmol) at room temperature. Then, this solution was cooled to 0° C. and mercuric chloride (6.05 g, 22.2 mmol) was added in two portions within a period of 10 min. After addition, the suspension was allowed to warm to room temperature and stirred for 15 h. The resulting black solids were filtered through a plug of celite and washed with dichloromethane (200 mL) and methanol (500 mL). The combined solvents were removed under the vacuum and the crude residue was diluted with water (150 mL) and ethyl acetate (150 mL). The two layers were separated and the aqueous layer was extracted with ethyl acetate (2×100 mL). The combined organic extracts were washed with brine solution and dried over anhydrous magnesium sulfate. Filtration of the drying agent and removal of the solvent under the vacuum gave the crude residue which was purified by using Biotage silica gel column chromatography to afford 1.0 g (19% yield) of 2-[2-(4-hydroxy-phenyl)-ethylamino]-thiazol-4-one as a white amorphous solid: HRES(+) m/e calcd for C10H8ClFN2OS (M+H)+237.0692, found 237.0693. After addition to warm to room temperature The resulting black solids were filtered through a plug of celite washed with dichloromethane (200 mL) and methanol (500 mL) The combined solvents were removed under the vacuum the crude residue was diluted with water (150 mL) and ethyl acetate (150 mL) The two layers were separated the aqueous layer was extracted with ethyl acetate (2×100 mL) The combined organic extracts were washed with brine solution dried over anhydrous magnesium sulfate Filtration of the drying agent and removal of the solvent under the vacuum gave the crude residue which was purified

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

実験手順: Two g of p-ethylaminophenol (0.0146 moles) were dissolved in 50 ml DMF. To this was added 2.98 g of acetic anhydride (0.0292 moles). The mixture was heated at 60° for three hours and then poured over crushed ice. Sodium carbonate was added until a pH of approximately 10 was achieved. The solution and precipitated oil were extracted with chloroform, dried over anhydrous magnesium sulfate, and then evaporated to dryness leaving a residual oil. To this oil was added 5% sodium hydroxide, and the mixture was heated at 60° for one hour. The solution was cooled and then extracted with chloroform. The remaining aqueous phase was acidified with dilute HCl to achieve a pH of approximately 4, and then extracted with chloroform. The liquid was dried over anhydrous magnesium sulfate, and then evaporated to dryness. The residual brown solid material was recrystallized from an ethanol-water mixture to yield N-ethyl-4'-hydroxyacetanilide (melting point 183°-185° C.). The mixture was heated at 60° for three hours poured over crushed ice The solution and precipitated oil were extracted with chloroform dried over anhydrous magnesium sulfate evaporated to dryness leaving a residual oil the mixture was heated at 60° for one hour The solution was cooled extracted with chloroform extracted with chloroform The liquid was dried over anhydrous magnesium sulfate evaporated to dryness The residual brown solid material was recrystallized from an ethanol-water mixture

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

実験手順: Two g of p-ethylaminophenol (0.0146 moles) were dissolved in 50 ml DMF. To this was added 2.98 g of acetic anhydride (0.0292 moles). The mixture was heated at 60° for three hours and then poured over crushed ice. Sodium carbonate was added until a pH of approximately 10 was achieved. The solution and precipitated oil were extracted with chloroform, dried over anhydrous magnesium sulfate, and then evaporated to dryness leaving a residual oil. To this oil was added 5% sodium hydroxide, and the mixture was heated at 60° for one hour. The solution was cooled and then extracted with chloroform. The remaining aqueous phase was acidified with dilute HCl to achieve a pH of approximately 4, and then extracted with chloroform. The liquid was dried over anhydrous magnesium sulfate, and then evaporated to dryness. The residual brown solid material was recrystallized from an ethanol-water mixture to yield N-ethyl-4'-hydroxyacetanilide (melting point 183°-185° C.). The mixture was heated at 60° for three hours poured over crushed ice The solution and precipitated oil were extracted with chloroform dried over anhydrous magnesium sulfate evaporated to dryness leaving a residual oil the mixture was heated at 60° for one hour The solution was cooled extracted with chloroform extracted with chloroform The liquid was dried over anhydrous magnesium sulfate evaporated to dryness The residual brown solid material was recrystallized from an ethanol-water mixture

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

実験手順: Five g of this 4-acetoxyacetanilide (0.0259 moles) was dissolved in 200 ml of dry tetrahydrofuran (THF). To this mixture was added slowly, over one-half hour, 1.97 g (0.0518 moles) of lithium aluminum hydride. After the addition of this reagent, the reaction was refluxed for three hours, cooled, and saturated ammonium chloride solution was slowly added. The resultant mixture was filtered, evaporated to dryness and the remaining oil was dissolved in dilute HCl. This solution was extracted with chloroform several times. The remaining aqueous phase was made basic with sodium carbonate to achieve approximately pH 10 and extracted once again with chloroform. The chloroform solution was dried over anhydrus magnesium sulfate and evaporated to dryness. This acid/base extraction procedure was repeated several time to yield 2.2 g of p-ethylaminophenol, as an oil which solidified upon standing. To this mixture was added slowly, over one-half hour After the addition of this reagent the reaction was refluxed for three hours cooled The resultant mixture was filtered evaporated to dryness the remaining oil was dissolved in dilute HCl This solution was extracted with chloroform several times extracted once again with chloroform The chloroform solution was dried over anhydrus magnesium sulfate evaporated to dryness This acid/base extraction procedure

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

実験手順: To a suspension of (4-hydroxy-phenyl)-ethylamine (3.14 g, 22.2 mmol) and Rhodanine (2.96 g, 22.2 mmol) in ethanol (314 mL) was added DIPEA (4.76 mL, 26.64 mmol) at room temperature. Then, this solution was cooled to 0° C. and mercuric chloride (6.05 g, 22.2 mmol) was added in two portions within a period of 10 min. After addition, the suspension was allowed to warm to room temperature and stirred for 15 h. The resulting black solids were filtered through a plug of celite and washed with dichloromethane (200 mL) and methanol (500 mL). The combined solvents were removed under the vacuum and the crude residue was diluted with water (150 mL) and ethyl acetate (150 mL). The two layers were separated and the aqueous layer was extracted with ethyl acetate (2×100 mL). The combined organic extracts were washed with brine solution and dried over anhydrous magnesium sulfate. Filtration of the drying agent and removal of the solvent under the vacuum gave the crude residue which was purified by using Biotage silica gel column chromatography to afford 1.0 g (19% yield) of 2-[2-(4-hydroxy-phenyl)-ethylamino]-thiazol-4-one as a white amorphous solid: HRES(+) m/e calcd for C10H8ClFN2OS (M+H)+237.0692, found 237.0693. After addition to warm to room temperature The resulting black solids were filtered through a plug of celite washed with dichloromethane (200 mL) and methanol (500 mL) The combined solvents were removed under the vacuum the crude residue was diluted with water (150 mL) and ethyl acetate (150 mL) The two layers were separated the aqueous layer was extracted with ethyl acetate (2×100 mL) The combined organic extracts were washed with brine solution dried over anhydrous magnesium sulfate Filtration of the drying agent and removal of the solvent under the vacuum gave the crude residue which was purified

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

実験手順: Two g of p-ethylaminophenol (0.0146 moles) were dissolved in 50 ml DMF. To this was added 2.98 g of acetic anhydride (0.0292 moles). The mixture was heated at 60° for three hours and then poured over crushed ice. Sodium carbonate was added until a pH of approximately 10 was achieved. The solution and precipitated oil were extracted with chloroform, dried over anhydrous magnesium sulfate, and then evaporated to dryness leaving a residual oil. To this oil was added 5% sodium hydroxide, and the mixture was heated at 60° for one hour. The solution was cooled and then extracted with chloroform. The remaining aqueous phase was acidified with dilute HCl to achieve a pH of approximately 4, and then extracted with chloroform. The liquid was dried over anhydrous magnesium sulfate, and then evaporated to dryness. The residual brown solid material was recrystallized from an ethanol-water mixture to yield N-ethyl-4'-hydroxyacetanilide (melting point 183°-185° C.). The mixture was heated at 60° for three hours poured over crushed ice The solution and precipitated oil were extracted with chloroform dried over anhydrous magnesium sulfate evaporated to dryness leaving a residual oil the mixture was heated at 60° for one hour The solution was cooled extracted with chloroform extracted with chloroform The liquid was dried over anhydrous magnesium sulfate evaporated to dryness The residual brown solid material was recrystallized from an ethanol-water mixture

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

実験手順: Five g of this 4-acetoxyacetanilide (0.0259 moles) was dissolved in 200 ml of dry tetrahydrofuran (THF). To this mixture was added slowly, over one-half hour, 1.97 g (0.0518 moles) of lithium aluminum hydride. After the addition of this reagent, the reaction was refluxed for three hours, cooled, and saturated ammonium chloride solution was slowly added. The resultant mixture was filtered, evaporated to dryness and the remaining oil was dissolved in dilute HCl. This solution was extracted with chloroform several times. The remaining aqueous phase was made basic with sodium carbonate to achieve approximately pH 10 and extracted once again with chloroform. The chloroform solution was dried over anhydrus magnesium sulfate and evaporated to dryness. This acid/base extraction procedure was repeated several time to yield 2.2 g of p-ethylaminophenol, as an oil which solidified upon standing. To this mixture was added slowly, over one-half hour After the addition of this reagent the reaction was refluxed for three hours cooled The resultant mixture was filtered evaporated to dryness the remaining oil was dissolved in dilute HCl This solution was extracted with chloroform several times extracted once again with chloroform The chloroform solution was dried over anhydrus magnesium sulfate evaporated to dryness This acid/base extraction procedure