2-氧代环辛酸甲酯

反应条件: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of methyl 2-oxocyclooctanecarboxylate (32.0 g, 174 mmol), methyl 3-amino-4-bromobenzoate (20.0 g, 87 mmol) and ethanol (120 mL) was heated to reflux, at an oil bath of 130° C., acetic acid (1.5 mL) was added and the mixture was reflux for 1.5 hours. Hot PPA (200 g, 120° C.) was added to the reaction mixture carefully. The reaction mixture was heated at an oil bath of 130° C. for 3 hours. After cooling for a while, ice (200 g), ethyl acetate (60 mL) and petroleum ether (60 mL) were added to the reaction mixture, the mixture was concentrated until 200 mL solvent was removed. Then water (600 mL) and ethyl acetate (60 mL) were added, the resulting mixture was stayed at room temperature overnight. A light brown solid was slowly formed. The mixture was filtered and the filtered cake was dried to give a light brown solid, which was placed into methanol (90 mL). SOCl2 (30 mL) was added dropwise with cooling with an ice-bath. The resulting mixture was heated to reflux for 4 hours, concentrated and treated with saturated NaHCO3 solution (60 mL) and ethyl acetate (30 mL), filtered and the filtered cake was dried to give desired product (6.6 g) as a pale white solid (21%). 1H NMR (DMSO-d6) δ10.25 (s, 1H), 7.96-7.98 (d, 1H, J=7.6 Hz), 7.09-7.11 (d, 1H, J=7.6 Hz), 3.02-3.06 (m, 2H), 2.63-2.66 (m, 2H), 1.75-1.77 (m, 2H), 1.53-1.55 (m, 2H), and 1.36-1.39 (m, 4H). MS (ESI) m/e [M+1]+ 364/366. was heated the mixture was reflux for 1.5 hours Hot PPA (200 g, 120° C.) was added to the reaction mixture carefully The reaction mixture was heated at an oil bath of 130° C. for 3 hours were added to the reaction mixture the mixture was concentrated until 200 mL solvent was removed Then water (600 mL) and ethyl acetate (60 mL) were added A light brown solid was slowly formed The mixture was filtered the filtered cake was dried to give a light brown solid, which with cooling with an ice-bath The resulting mixture was heated to reflux for 4 hours concentrated treated with saturated NaHCO3 solution (60 mL) and ethyl acetate (30 mL) filtered the filtered cake was dried

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

实验步骤: To a solution of dimethyl carbonate (30 mL, 0.36 mol) in dry THF (600 mL) was added sodium hydride (15 g, 0.36 mol) by portion at 5-10° C. The resulting mixture was stirred at this temperature for 30 min and then was added a solution of cyclooctanone (15.0 g, 0.12 mol) in THF (100 mL) dropwise over 30 min. The resultant mixture was stirred at refluxed for 4 h before cooling to room temperature. The reaction mixture was poured into saturated NaHCO3 solution (100 mL) and ice (500 g), and then the mixture was extracted with PE/EA (4:1, 400 mL×2). The organic layer was washed with brine (400 mL), dried over Na2SO4 and concentrated to give crude product. Then the target product (19.3 g, 88%) was purified by distilling at 60° C. in vacuum. at refluxed for 4 h the mixture was extracted with PE/EA (4:1, 400 mL×2) The organic layer was washed with brine (400 mL) dried over Na2SO4 concentrated to give crude product Then the target product (19.3 g, 88%) was purified by distilling at 60° C. in vacuum

反应条件: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of methyl 2-oxocyclooctanecarboxylate (32.0 g, 174 mmol), methyl 3-amino-4-bromobenzoate (20.0 g, 87 mmol) and ethanol (120 mL) was heated to reflux, at an oil bath of 130° C., acetic acid (1.5 mL) was added and the mixture was reflux for 1.5 hours. Hot PPA (200 g, 120° C.) was added to the reaction mixture carefully. The reaction mixture was heated at an oil bath of 130° C. for 3 hours. After cooling for a while, ice (200 g), ethyl acetate (60 mL) and petroleum ether (60 mL) were added to the reaction mixture, the mixture was concentrated until 200 mL solvent was removed. Then water (600 mL) and ethyl acetate (60 mL) were added, the resulting mixture was stayed at room temperature overnight. A light brown solid was slowly formed. The mixture was filtered and the filtered cake was dried to give a light brown solid, which was placed into methanol (90 mL). SOCl2 (30 mL) was added dropwise with cooling with an ice-bath. The resulting mixture was heated to reflux for 4 hours, concentrated and treated with saturated NaHCO3 solution (60 mL) and ethyl acetate (30 mL), filtered and the filtered cake was dried to give desired product (6.6 g) as a pale white solid (21%). 1H NMR (DMSO-d6) δ10.25 (s, 1H), 7.96-7.98 (d, 1H, J=7.6 Hz), 7.09-7.11 (d, 1H, J=7.6 Hz), 3.02-3.06 (m, 2H), 2.63-2.66 (m, 2H), 1.75-1.77 (m, 2H), 1.53-1.55 (m, 2H), and 1.36-1.39 (m, 4H). MS (ESI) m/e [M+1]+ 364/366. was heated the mixture was reflux for 1.5 hours Hot PPA (200 g, 120° C.) was added to the reaction mixture carefully The reaction mixture was heated at an oil bath of 130° C. for 3 hours were added to the reaction mixture the mixture was concentrated until 200 mL solvent was removed Then water (600 mL) and ethyl acetate (60 mL) were added A light brown solid was slowly formed The mixture was filtered the filtered cake was dried to give a light brown solid, which with cooling with an ice-bath The resulting mixture was heated to reflux for 4 hours concentrated treated with saturated NaHCO3 solution (60 mL) and ethyl acetate (30 mL) filtered the filtered cake was dried

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

实验步骤: To a solution of dimethyl carbonate (30 mL, 0.36 mol) in dry THF (600 mL) was added sodium hydride (15 g, 0.36 mol) by portion at 5-10° C. The resulting mixture was stirred at this temperature for 30 min and then was added a solution of cyclooctanone (15.0 g, 0.12 mol) in THF (100 mL) dropwise over 30 min. The resultant mixture was stirred at refluxed for 4 h before cooling to room temperature. The reaction mixture was poured into saturated NaHCO3 solution (100 mL) and ice (500 g), and then the mixture was extracted with PE/EA (4:1, 400 mL×2). The organic layer was washed with brine (400 mL), dried over Na2SO4 and concentrated to give crude product. Then the target product (19.3 g, 88%) was purified by distilling at 60° C. in vacuum. at refluxed for 4 h the mixture was extracted with PE/EA (4:1, 400 mL×2) The organic layer was washed with brine (400 mL) dried over Na2SO4 concentrated to give crude product Then the target product (19.3 g, 88%) was purified by distilling at 60° C. in vacuum