4-bromo-2,3-dihydroinden-1-one

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

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 4-bromo-1-indanone (1.0 g) in a mixture of ethanol (6 ml) and tetrahydrofuran (3 ml) was added sodium borohydride (0.09 g) at an ice temperature. The reaction mixture was stirred at the same temperature overnight and poured into dilute hydrochloric acid, and the aqueous layer was saturated with saline and extracted with ether. The organic layer was washed with a saturated aqueous saline, dried over sodium sulfate, and the solvent was removed by distillation under reduced pressure. The residual concentrate (1.02 g) thus obtained was used for the next reaction without further purification. extracted with ether The organic layer was washed with a saturated aqueous saline dried over sodium sulfate the solvent was removed by distillation under reduced pressure The residual concentrate (1.02 g) thus obtained was used for the next reaction without further purification

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

実験手順: Thionyl chloride (85 ml) was added to 3-(2-bromophenyl)propionic acid (16.88 g), and the mixture was stirred under reflux for 2 hours. After the mixture was left standing for cooling, the excessive amount of the thionyl chloride was removed by distillation under reduced pressure, and the residual mixture was distilled azeotropically once with toluene and once with carbon tetrachloride. The residual concentrate was dissolved in carbon tetrachloride (30 ml) and added at a temperature of 5°-10° C. dropwise to a suspension of aluminum chloride (14.74 g) in carbon tetrachloride (100 ml). The mixture was stirred at the same temperature for 40 minutes, then at room temperature for 30 minutes and further under reflux for 1 hour. After left standing for cooling, the mixture was poured into ice-hydrochloric acid, and extracted with methylene chloride. The organic layer was washed with dilute hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous saline, and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the residual concentrate was purified by chromatography on a silica gel column to give the title compound (13.2 g). under reflux for 2 hours After the mixture was left for cooling the excessive amount of the thionyl chloride was removed by distillation under reduced pressure the residual mixture was distilled azeotropically once with toluene and once with carbon tetrachloride The residual concentrate was dissolved in carbon tetrachloride (30 ml) added at a temperature of 5°-10° C. dropwise to a suspension of aluminum chloride (14.74 g) in carbon tetrachloride (100 ml) The mixture was stirred at the same temperature for 40 minutes further under reflux for 1 hour After left standing for cooling the mixture was poured into ice-hydrochloric acid extracted with methylene chloride The organic layer was washed with dilute hydrochloric acid a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous saline, and dried over sodium sulfate The solvent was removed by distillation under reduced pressure the residual concentrate was purified by chromatography on a silica gel column

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred mixture of sodium azide (862 mg, 13.3 mmol) in H2O (1.7 mL) and CHCl3 (6.5 mL) was added conc. H2SO4 (0.23 mL, 4.14 mmol). The reaction mixture was stirred vigorously at 0° C. for 2.5 h. The CHCl3 layer was separated, dried over Na2SO4, and added to a solution of 4-bromo-1-indanone (1.12 g, 5.31 mmol) in CHCl3 (20 mL). To this mixture was added conc. H2SO4 (1.75 mL, 31.5 mmol) dropwise over 10 min. The reaction mixture was heated at 45 C for 1 h then poured into ice-water, neutralized with 20% aqueous NaOH, and extracted with CH2Cl2 (100 mL). The organic extract was dried over Na2SO4, filtered, and concentrated in vacuo. The crude product was purified by silica gel chromatography, eluting with a gradient of CH2Cl2:EtOAc—100:0 to 80:20, to give the title compound. MS: m/z=226 (M+1). The CHCl3 layer was separated dried over Na2SO4 The reaction mixture was heated at 45 C for 1 h extracted with CH2Cl2 (100 mL) The organic extract was dried over Na2SO4 filtered concentrated in vacuo The crude product was purified by silica gel chromatography eluting with a gradient of CH2Cl2