| 82% |
With copper(ll) bromide; In chloroform; ethyl acetate; at 60℃; for 0.333333h; |
A three-necked flask was charged with 15 g (73.5 mmol) of <strong>[37148-48-4]4-amino-3,5-dichloroacetophenone</strong>,33 g (147 mmol) of copper bromide,225 mL of ethyl acetate, 225 mL of chloroform,60 heating reflux 20min,Then, 75 mL of absolute ethanol was added and the reaction was continued to reflux. The mixture gradually turned from black to green, and a large amount of white precipitate formed. After 2 h, the reaction was stopped,Filtered while hot, the filter cake was washed with chloroform, the filtrate was washed with water until no white precipitate, dried over anhydrous sodium sulfate, dried to give a pale yellow solid, silica gel column chromatography to give a white solidAmino-3,5-dichloro-bromoacetophenone 217 g, yield 82%. |
| 80% |
|
To a vial was added chloroform (120 mL) and <strong>[37148-48-4]1-(4-amino-3,5-dichlorophenyl)ethanone</strong> (6.12 g, 30 mmol). The mixtures wereheated to reflux and then bromine (2.04 ml, 39 mmol) was slowlyadded. The mixture was stirred for 15 min and then cooled to roomtemperature. The solvent was evaporated to afford the crudeproduct. Then crude product was dissolved in THF (120 ml), andcooled to 0 C. To the solution was slowly added a solution ofdiethylphosphite (0.51 ml, 4 mmol) and triethylamine (TEA, 3.3 ml,24 mmol) in THF (30 ml). The mixture was warmed to room temperatureand stirred for 10 min. After completion of the reaction,the mixturewas concentrated in vacuo and poured into crushed ice.The precipitatewas filtered out,washed withwater and air-dried togive the pure product 6g as light brown solid (6.78 g, 80% yield). m.p. 140e141 C; 1H NMR (400 MHz, DMSO-d6) d 7.88 (s, 2H), 6.60(s, 2H), 4.79 (s, 2H); MS (ESI) m/z calcd for C8H7BrCl2NO [M H]281.91, found 281.88. |
| 80% |
|
The starting material, <strong>[37148-48-4]4-amino-3,5-dichloroacetophenone</strong> (1020 mg, 5 mmol) was dissolved in chloroform (20 ml) and liquid bromine (0.34 ml, 6.5 mmol) was added under reflux. After refluxing for 15 min, it was cooled to room temperature, the solvent was evaporated under reduced pressure, dissolved in THF (20 ml) and cooled to 0C. Diethyl phosphite (0.51 ml, 4 mmol) and TEA (0.55 ml, 4 mmol) in THF (5 ml) were added slowly. Slowly warm to room temperature and stir for 10 min. Concentrate under reduced pressure and pour into ice water. Filter, dry, recrystallize with a suitable solvent. Obtained light yellow solid, yield 80%. |
| 75% |
With copper(ll) bromide; In ethanol; chloroform; ethyl acetate; for 2h;Reflux; |
4.8 g (23.7 mmol) of <strong>[37148-48-4]4-amino-3,5-dichloroacetophenone</strong> was weighed into a 250 ml round bottom flask, and 60 ml of EA (ethyl acetate), 60 ml of CHCl3 and 20 ml of CH3CH2OH solvent were added thereto, and the mixture was stirred and dissolved at reflux temperature.Weigh 7.8 g (35 mmol) of copper(II) bromide and add it to the reaction unit.A total of 2h reaction. Hot and suction filtration,Wash the filter cake 3 times with 20 ml of CH2Cl2 each time.The filtrate was transferred to a separatory funnel, and the filtrate was washed with 3 times of 50 ml of pure water.The organic phase was collected and dried over anhydrous sodium sulfate.After filtration, spin dry the solvent.Recrystallization from 5.0 g of ethanol 75% by weight 4-amino-3,5-dichlorobromoacetophenone. |
| 72% |
With bromine; In chloroform; at 20℃; for 1h; |
4-Amino-3,5-dichloro-bromoacetophenone (2)Bromine (5 ml, 98 mmol) was added to a mixture of 4-amino-3,5- dichloroacetophenone (1) (20 g, 98 mmol) in CHCI3 (240 ml) at room temperature. The mixture was stirred for 1 h then EtOH (40 ml) was added. The mixture was cooled to 00C and stirred for 1 h. The precipitate was filtered and air-dried (20.4 g, 72%). 1H NMR (400 MHz, DMSO): 4.77 (2H, s), 6.61 (2H, bs), 7.86 (2H, s); 13C NMR (100 MHz, DMSO): 63.39, 117.89, 128.57, 129.75, 146.17, 195.99. |
| 67% |
With bromine; In chloroform; at 20℃; for 1h; |
Bromine (63 ml, 1.22 mol) was added to a mixture of 4-amino-3,5- dichloroacetophenone (1) (250 g, 1.22 mol) in CHCI3 (3 L ml) at room temperature. The mixture was stirred for 1 h then EtOH (500 ml) was added. The mixture was cooled to 00C and stirred for 1 h. The precipitate was filtered and air-dried (4.7 g,67%).1H NMR (400 MHz, DMSO): 4.77 (2H, s), 6.61 (2H, bs), 7.86 (2H, s); 13C NMR (100MHz, DMSO): 63.39, 117.89, 128.57, 129.75, 146.17, 195.99. |
| 62% |
With copper bromide; In chloroform; ethyl acetate; for 4h;Reflux; |
To a 250 ml three-necked flask, 4.8 g of <strong>[37148-48-4]3,5-dichloro-4-aminoacetophenone</strong>, 10.8 g of copper bromide, 48 ml of ethyl acetate and 48 ml of chloroform were added, and the mixture was refluxed for 4 hours. After filtration, the cake was washed with ethyl acetate, and the filtrate was combined, washed twice with water, brine, and brine. The solid was dried to obtain 4.0 g of solid 3,5-dichloro-4-amino-alpha-bromoacetophenone in a yield of about 62% |
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