(2-amino-5-chlorophenyl)-(4-hydroxyphenyl)methanone

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

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

Procedure: A solution was formed by dissolving 2-amino-5-chloro-4'-hydroxybenzophenone (1.72 g, 8.07 mmol) in 40 mL of DMF. Potassium bis(trimethylsilyl)amide that was 0.5M in toluene (16.1 mL, 8.07 mmol, 1.0 equivalents) was added dropwise with stirring. Allyl 2-(4-bromomethylphenoxy)acetate (2.30 g, 8.07 mmol, 1.0 equivalents) was then added and the resulting orange slurry was stirred at ambient temperature for 45 minutes. The slurry was concentrated in vacuo, then diluted with CH2Cl2 (150 mL) and was extracted with 1N aqueous sodium bicarbonate (100 mL) and with 1N aqueous sodium chloride (100 mL), then dried over sodium sulfate and concentrated in vacuo to give the product as a yellow solid which was approximately 95% pure and was taken to the next step without purification. The product had Rf of 0.55 in 50:50:2 ethyl acetate/hexane/triethylamine. The structure was confirmed by proton NMR, carbon-13 NMR, and electron impact mass spectroscopy. A solution was formed was added dropwise the resulting orange slurry was stirred at ambient temperature for 45 minutes The slurry was concentrated in vacuo diluted with CH2Cl2 (150 mL) was extracted with 1N aqueous sodium bicarbonate (100 mL) and with 1N aqueous sodium chloride (100 mL) dried over sodium sulfate concentrated in vacuo

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

Procedure: A solution was formed by dissolving 2-amino-5-chloro-4'-hydroxybenzophenone (1.72 g, 8.07 mmol) in 40 mL of DMF. Potassium bis(trimethylsilyl)amide that was 0.5M in toluene (16.1 mL, 8.07 mmol, 1.0 equivalents) was added dropwise with stirring. Allyl 2-(4-bromomethylphenoxy)acetate (2.30 g, 8.07 mmol, 1.0 equivalents) was then added and the resulting orange slurry was stirred at ambient temperature for 45 minutes. The slurry was concentrated in vacuo, then diluted with CH2Cl2 (150 mL) and was extracted with 1N aqueous sodium bicarbonate (100 mL) and with 1N aqueous sodium chloride (100 mL), then dried over sodium sulfate and concentrated in vacuo to give the product as a yellow solid which was approximately 95% pure and was taken to the next step without purification. The product had Rf of 0.55 in 50:50:2 ethyl acetate/hexane/triethylamine. The structure was confirmed by proton NMR, carbon-13 NMR, and electron impact mass spectroscopy. A solution was formed was added dropwise the resulting orange slurry was stirred at ambient temperature for 45 minutes The slurry was concentrated in vacuo diluted with CH2Cl2 (150 mL) was extracted with 1N aqueous sodium bicarbonate (100 mL) and with 1N aqueous sodium chloride (100 mL) dried over sodium sulfate concentrated in vacuo

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

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

Procedure: A solution of 41 g (0.165 mole) 2-amino-5-chloro-4'-hydroxybenzophenone in 800 ml of ether and 200 ml of water was cooled to 5°. The mixture was stirred while 20 ml (0.277 mole) of bromoacetyl bromide and a 20% solution of sodium carbonate were added alternately keeping the solution slightly basic. After 20 min. the reaction mixture was filtered to collect 60 g (about 100%) of product mp 201°-202°. Recrystallization from ethanol gave colorless prisms, mp 201°-203°. After 20 min. the reaction mixture was filtered to collect 60 g (about 100%) of product mp 201°-202° Recrystallization from ethanol gave colorless prisms, mp 201°-203°

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

Procedure: To a solution of 83.7 g (0.34 mole) of 5-chloro-3-(4-hydroxyphenyl)-2,1-benzisoxazole in 1500 ml of glacial acetic acid was added 45 g of iron filings. The mixture was stirred and heated on the steam bath for 20 min. Every 30 min. an additional 20 g of iron filings and 100 ml of water was added for 2.5 hr. After 30 min. more, the reaction mixture was filtered while hot. The collected precipitate was heated with acetic acid and filtered. The combined filtrates were diluted with ice water to precipitate 39.8 g (47%) of product, mp 170°-175°. Recrystallization from methanol-water gave yellow rods, mp 173°-178°. heated on the steam bath for 20 min the reaction mixture was filtered while hot The collected precipitate was heated with acetic acid filtered The combined filtrates were diluted with ice water to precipitate 39.8 g (47%) of product, mp 170°-175° Recrystallization from methanol-water gave yellow rods, mp 173°-178°

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

Procedure: A solution was formed by dissolving 2-amino-5-chloro-4'-hydroxybenzophenone (1.72 g, 8.07 mmol) in 40 mL of DMF. Potassium bis(trimethylsilyl)amide that was 0.5M in toluene (16.1 mL, 8.07 mmol, 1.0 equivalents) was added dropwise with stirring. Allyl 2-(4-bromomethylphenoxy)acetate (2.30 g, 8.07 mmol, 1.0 equivalents) was then added and the resulting orange slurry was stirred at ambient temperature for 45 minutes. The slurry was concentrated in vacuo, then diluted with CH2Cl2 (150 mL) and was extracted with 1N aqueous sodium bicarbonate (100 mL) and with 1N aqueous sodium chloride (100 mL), then dried over sodium sulfate and concentrated in vacuo to give the product as a yellow solid which was approximately 95% pure and was taken to the next step without purification. The product had Rf of 0.55 in 50:50:2 ethyl acetate/hexane/triethylamine. The structure was confirmed by proton NMR, carbon-13 NMR, and electron impact mass spectroscopy. A solution was formed was added dropwise the resulting orange slurry was stirred at ambient temperature for 45 minutes The slurry was concentrated in vacuo diluted with CH2Cl2 (150 mL) was extracted with 1N aqueous sodium bicarbonate (100 mL) and with 1N aqueous sodium chloride (100 mL) dried over sodium sulfate concentrated in vacuo

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

Procedure: A solution of 41 g (0.165 mole) 2-amino-5-chloro-4'-hydroxybenzophenone in 800 ml of ether and 200 ml of water was cooled to 5°. The mixture was stirred while 20 ml (0.277 mole) of bromoacetyl bromide and a 20% solution of sodium carbonate were added alternately keeping the solution slightly basic. After 20 min. the reaction mixture was filtered to collect 60 g (about 100%) of product mp 201°-202°. Recrystallization from ethanol gave colorless prisms, mp 201°-203°. After 20 min. the reaction mixture was filtered to collect 60 g (about 100%) of product mp 201°-202° Recrystallization from ethanol gave colorless prisms, mp 201°-203°

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

Procedure: To a solution of 83.7 g (0.34 mole) of 5-chloro-3-(4-hydroxyphenyl)-2,1-benzisoxazole in 1500 ml of glacial acetic acid was added 45 g of iron filings. The mixture was stirred and heated on the steam bath for 20 min. Every 30 min. an additional 20 g of iron filings and 100 ml of water was added for 2.5 hr. After 30 min. more, the reaction mixture was filtered while hot. The collected precipitate was heated with acetic acid and filtered. The combined filtrates were diluted with ice water to precipitate 39.8 g (47%) of product, mp 170°-175°. Recrystallization from methanol-water gave yellow rods, mp 173°-178°. heated on the steam bath for 20 min the reaction mixture was filtered while hot The collected precipitate was heated with acetic acid filtered The combined filtrates were diluted with ice water to precipitate 39.8 g (47%) of product, mp 170°-175° Recrystallization from methanol-water gave yellow rods, mp 173°-178°

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

Procedure: A solution was formed by dissolving 2-amino-5-chloro-4'-hydroxybenzophenone (1.72 g, 8.07 mmol) in 40 mL of DMF. Potassium bis(trimethylsilyl)amide that was 0.5M in toluene (16.1 mL, 8.07 mmol, 1.0 equivalents) was added dropwise with stirring. Allyl 2-(4-bromomethylphenoxy)acetate (2.30 g, 8.07 mmol, 1.0 equivalents) was then added and the resulting orange slurry was stirred at ambient temperature for 45 minutes. The slurry was concentrated in vacuo, then diluted with CH2Cl2 (150 mL) and was extracted with 1N aqueous sodium bicarbonate (100 mL) and with 1N aqueous sodium chloride (100 mL), then dried over sodium sulfate and concentrated in vacuo to give the product as a yellow solid which was approximately 95% pure and was taken to the next step without purification. The product had Rf of 0.55 in 50:50:2 ethyl acetate/hexane/triethylamine. The structure was confirmed by proton NMR, carbon-13 NMR, and electron impact mass spectroscopy. A solution was formed was added dropwise the resulting orange slurry was stirred at ambient temperature for 45 minutes The slurry was concentrated in vacuo diluted with CH2Cl2 (150 mL) was extracted with 1N aqueous sodium bicarbonate (100 mL) and with 1N aqueous sodium chloride (100 mL) dried over sodium sulfate concentrated in vacuo

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