甲基5-溴-2-(1-溴乙基)苯甲酸盐

反应条件: temp:67.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Add solid methyl 5-bromo-2-(1-bromoethyl)benzoate (1724 g, 5.35 mol) to a solution of commercially available (R)-1-(4-methoxyphenyl)ethanamine (BePharm, WZG111219-071; 974 g, 6.44 mol) and triethylamine (1710 mL, 12.26 mol) in methanol (12 L). Heat the mixture for 10 hours at 67° C. then evaporate to dryness under reduced pressure. Partition the residue with ethyl acetate (5 L) and aqueous 1 N HCl (10 L), separate the phases, wash the organic phase again with aqueous 1 N HCl (5 L), saturated sodium bicarbonate, saturated aqueous sodium chloride, then dry over sodium sulfate, filter, and evaporate under reduced pressure. Dissolve the dark red oil in methyl-tert-butyl ether (750 mL) and add petroleum ether (3 L) with vigorous stirring. Filter the solids, wash with methyl-tert-butyl ether/petroleum ether (1:8), petroleum ether, dry in open air to give the title compound as an off-white solid (1014 g, 52%). ES/MS m/z: 360 (M+H). then evaporate to dryness under reduced pressure Partition the residue with ethyl acetate (5 L) and aqueous 1 N HCl (10 L) separate the phases wash the organic phase again with aqueous 1 N HCl (5 L), saturated sodium bicarbonate, saturated aqueous sodium chloride dry over sodium sulfate filter evaporate under reduced pressure Dissolve the dark red oil in methyl-tert-butyl ether (750 mL) add petroleum ether (3 L) with vigorous stirring Filter the solids wash with methyl-tert-butyl ether/petroleum ether (1:8), petroleum ether dry in open air

反应条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Add N-bromosuccinimide (1090 g, 6.12 mol) and 2,2′-azo-bis-isobutyronitrile (11.4 g, 0.069 mol) to a 20° C. solution of methyl 5-bromo-2-ethylbenzoate (1296 g, 5.33 mol) in carbon tetrachloride (7 L). Heat to reflux for 4 hours, cool to 20-30° C. and wash with water (10 L), extract the aqueous phase with dichloromethane (5 L), combine the organic layers, and wash with water (10 L), Na2SO3 (5 L) and saturated aqueous sodium chloride. Dry with sodium sulfate, filter, and evaporate under reduced pressure to give the title compound as a pale yellow solid (1791 g, 104% crude). ES/MS m/z: 241 (M−HBr). Heat to reflux for 4 hours wash with water (10 L) extract the aqueous phase with dichloromethane (5 L) wash with water (10 L), Na2SO3 (5 L) and saturated aqueous sodium chloride Dry with sodium sulfate filter evaporate under reduced pressure