N-[2-(2-bromoacetyl)phenyl]acetamide

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: 31 g (0.175 mol) of N-(2-Acetylphenyl)-acetamide (prepared by acylation of 2-aminoacetophenone with acetyl chloride as described by Fuerstner, Alois; Jumbam, Denis N.; Tetrahedron; 48; 29; 5991-6010, (1992)) was dissolved in 200 ml of glacial acetic acid. 127 ml of 33% strength HBr in glacial acetic acid was added and then, at room temperature, 8.75 ml (0.175 mol) of bromine was slowly run in. The mixture was stirred at room temperature overnight. The mixture was stirred into 1.5 l of ice-water, and the precipitated product was filtered off with suction, thoroughly washed with ice-water and dried in vacuo. The crude product contained, according to HPLC and NMR, some precursor and dibrominated product, but was pure enough (about 85% strength) for further reaction. at room temperature the precipitated product was filtered off with suction thoroughly washed with ice-water dried in vacuo for further reaction

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: To a solution of 26.3 g (0.138 mol) of 4-amino-1-(phenylmethyl)piperidine and 17.8 g (0.138 mol) of DIEA in 300 ml of dichloromethane was added dropwise a solution of 35.4 g (0.138 mol) of 1-[2-(acetylamino)phenyl]-2-bromoethanone in 150 ml of dichloromethane and the mixture was kept for a further 2 hours at room temperature. With external cooling with ice 13.5 g (0.20 mol) of sodium cyanate and 12 ml of glacial acetic acid were then added and the mixture was stirred overnight in a thawing ice bath. It was washed with water and saturated sodium hydrogen carbonate solution, dried over sodium sulphate and freed from solvent. The residue was triturated with 50 ml of ethyl acetate-methanol mixture (9/1 v/v), the resulting crystals were suction filtered, washed with ethyl acetate and dried in vacuo. 37.0 g (68.7% of theory) of colourless crystals were obtained, Rf=0.41 (eluant: dichloromethane/methanol 9/1 v/v). were then added It was washed with water and saturated sodium hydrogen carbonate solution dried over sodium sulphate The residue was triturated with 50 ml of ethyl acetate-methanol mixture (9/1 v/v) filtered washed with ethyl acetate dried in vacuo 37.0 g (68.7% of theory) of colourless crystals were obtained

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

実験手順: 45.0 g (0.282 mol) of dry bromine were added dropwise to a boiling solution of 50.0 g (0.282 mol) of 1-[2-(acetylamino)phenyl]ethanone in 400 ml of chloroform at room temperature. The solvent was distilled off, the residue was distributed between dichloromethane and saturated ice-cold sodium hydrogen carbonate solution. The organic phase was dried over sodium sulphate, evaporated down in vacuo, the residue was triturated with diethylether and suction filtered. After drying in vacuo 35.4 g (49% of theory) of colourless crystals were obtained, Rf=0.48 (eluant: petroleum ether/ethyl acetate 2/1 v/v). The solvent was distilled off The organic phase was dried over sodium sulphate evaporated down in vacuo the residue was triturated with diethylether and suction filtered After drying in vacuo 35.4 g (49% of theory) of colourless crystals were obtained

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

実験手順: To a solution of 26.3 g (0.138 mol) of 4-amino1-(phenylmethyl)piperidine and 17.8 g (0.138 mol) of DIEA in 300 ml of dichloromethane was added dropwise a solution of 35.4 g (0.138 mol) of 1-[2-(acetylamino)phenyl]-2-bromoethanone in 150 ml of dichloromethane and the mixture was kept for a further 2 hours at room temperature. With external cooling with ice 13.5 g (0.20 mol) of sodium cyanate and 12 ml of glacial acetic acid were then added and the mixture was stirred overnight in a thawing ice bath. It was washed with water and saturated sodium hydrogen carbonate solution, dried over sodium sulphate and freed from solvent. The residue was triturated with 50 ml of ethyl acetate-methanol mixture (9/1 v/v), the resulting crystals were suction filtered, washed with ethyl acetate and dried in vacuo. 37.0 g (68.7% of theory) of colourless crystals were obtained, Rf=0.41 (eluant: dichloromethane/methanol 9/1 v/v) were then added It was washed with water and saturated sodium hydrogen carbonate solution dried over sodium sulphate The residue was triturated with 50 ml of ethyl acetate-methanol mixture (9/1 v/v) filtered washed with ethyl acetate dried in vacuo 37.0 g (68.7% of theory) of colourless crystals were obtained

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

実験手順: 31 g (0.175 mol) of N-(2-acetylphenyl)acetamide (prepared by acylating 2-aminoacetophenone with acetyl chloride according to Fuerstner, Alois; Jumbam, Denis N.; Tetrahedron; 48; 29; 5991-6010, (1992)) were dissolved in 200 ml of glacial acetic acid. 127 ml of 33% HBr in glacial acetic acid were added and then 8.75 ml (0.175 mol) of bromine were added slowly at room temperature. The mixture was stirred at room temperature overnight. The mixture was stirred into 1.5 l of ice-water, and the precipitated product was filtered off with suction, washed thoroughly with ice-water and dried in vacuo. According to HPLC and NMR, the crude product contained some reactant and dibrominated product, but was clean enough for the further reaction (approx. 85%). the precipitated product was filtered off with suction washed thoroughly with ice-water dried in vacuo was clean enough for the further reaction (approx. 85%)

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

実験手順: 31 g (0.175 mol) of N-(2-Acetylphenyl)-acetamide (prepared by acylation of 2-aminoacetophenone with acetyl chloride as described by Fuerstner, Alois; Jumbam, Denis N.; Tetrahedron; 48; 29; 5991-6010, (1992)) was dissolved in 200 ml of glacial acetic acid. 127 ml of 33% strength HBr in glacial acetic acid was added and then, at room temperature, 8.75 ml (0.175 mol) of bromine was slowly run in. The mixture was stirred at room temperature overnight. The mixture was stirred into 1.5 l of ice-water, and the precipitated product was filtered off with suction, thoroughly washed with ice-water and dried in vacuo. The crude product contained, according to HPLC and NMR, some precursor and dibrominated product, but was pure enough (about 85% strength) for further reaction. at room temperature the precipitated product was filtered off with suction thoroughly washed with ice-water dried in vacuo for further reaction