反应 #2545
ord-b9a7125374424a33a8c178a8e25b8efd
反应方程式
反应物
试剂
反应条件
后处理
- 1温度heated
- 2温度under reflux for 4 hours
- 3浓缩After concentrating the reaction solution to 1/3 volume, insoluble materials
- 4其他were removed by filtration
- 5温度To the resulting filtrate cooled in an ice bath
- 6其他The resulting reaction mixture
- 7萃取extracted with methylene chloride
- 8洗涤washed with 10% citric acid aqueous solution, water and saturated brine in that order
- 9干燥After drying on anhydrous magnesium sulfate
- 10其他removing the solvent
- 11其他by evaporation
- 12其他to obtain creamy-colored powder
- 13workup.ADDITIONTo this were added
- 14温度of heating
- 15温度under reflux
- 16过滤filtering off the formed insoluble materials
- 17其他the organic solvent was removed by evaporation
- 18萃取The resulting residue was extracted with ethyl acetate
- 19洗涤the organic layer was washed with saturated brine
- 20干燥dried on anhydrous magnesium sulfate
- 21其他followed by the removal of the solvent by evaporation
- 22其他to obtain an orange oily material
- 23workup.STIRRINGAfter 1 hour of stirring at the same temperature
- 24温度warmed to room temperature
- 25其他After removing methanol
- 26其他by evaporation, ethyl acetate extraction
- 27洗涤the resulting organic layer was washed with saturated brine
- 28干燥dried on anhydrous magnesium sulfate
- 29其他subjected to evaporation
- 30其他to remove the solvent
- 31洗涤the resulting colorless solid material was washed with an ether-hexane (2:1) mixture solution
实验过程
N-Bromosuccinimide (1.29 g, 7.2 mmol) and AIBN (50 mg, 0.30 mmol) were suspended in carbon tetrachloride (80 ml), mixed with m-toluyl chloride (0.8 ml, 6.0 mmol) and then heated under reflux for 4 hours while exposing to light. After concentrating the reaction solution to 1/3 volume, insoluble materials were removed by filtration. To the resulting filtrate cooled in an ice bath were added dropwise o-anisidine (0.69 ml, 6 mmol) and 20% sodium hydroxide aqueous solution (5 ml) in that order. The resulting reaction mixture was stirred for 20 minutes at room temperature, extracted with methylene chloride and then washed with 10% citric acid aqueous solution, water and saturated brine in that order. After drying on anhydrous magnesium sulfate and removing the solvent by evaporation, the resulting light beige solid material was subjected to silica gel column chromatography (ether:hexane=1:1) to obtain creamy-colored powder. To this were added precipitated calcium carbonate (2.34 g, 23.4 mmol) and a dioxane-water (1:1) mixture solution (20 ml), followed by 6 hours of heating under reflux. After adding THF (50 ml) and filtering off the formed insoluble materials, the organic solvent was removed by evaporation. The resulting residue was extracted with ethyl acetate, and the organic layer was washed with saturated brine and dried on anhydrous magnesium sulfate, followed by the removal of the solvent by evaporation to obtain an orange oily material. This was dissolved in methanol (15 ml), and sodium borohydride (90 mg, 2.34 mmol) was added to the solution in one portion at -15° C. After 1 hour of stirring at the same temperature, the reaction mixture was mixed with acetone (1 ml), warmed to room temperature and then mixed with saturated ammonium chloride aqueous solution (10 ml). After removing methanol by evaporation, ethyl acetate extraction was carried out, and the resulting organic layer was washed with saturated brine, dried on anhydrous magnesium sulfate and then subjected to evaporation to remove the solvent. The thus obtained residue was subjected to silica gel column chromatography (ether:hexane=3:1), and the resulting colorless solid material was washed with an ether-hexane (2:1) mixture solution to obtain 1.02 g (66.1%) of the title compound in the form of colorless powder.