反応 #2545
ord-b9a7125374424a33a8c178a8e25b8efd
反応方程式
反応物
試薬
反応条件
後処理
- 1温度heated
- 2温度under reflux for 4 hours
- 3濃縮After concentrating the reaction solution to 1/3 volume, insoluble materials
- 4その他were removed by filtration
- 5温度To the resulting filtrate cooled in an ice bath
- 6その他The resulting reaction mixture
- 7抽出extracted with methylene chloride
- 8洗浄washed with 10% citric acid aqueous solution, water and saturated brine in that order
- 9乾燥After drying on anhydrous magnesium sulfate
- 10その他removing the solvent
- 11その他by evaporation
- 12その他to obtain creamy-colored powder
- 13workup.ADDITIONTo this were added
- 14温度of heating
- 15温度under reflux
- 16ろ過filtering off the formed insoluble materials
- 17その他the organic solvent was removed by evaporation
- 18抽出The resulting residue was extracted with ethyl acetate
- 19洗浄the organic layer was washed with saturated brine
- 20乾燥dried on anhydrous magnesium sulfate
- 21その他followed by the removal of the solvent by evaporation
- 22その他to obtain an orange oily material
- 23workup.STIRRINGAfter 1 hour of stirring at the same temperature
- 24温度warmed to room temperature
- 25その他After removing methanol
- 26その他by evaporation, ethyl acetate extraction
- 27洗浄the resulting organic layer was washed with saturated brine
- 28乾燥dried on anhydrous magnesium sulfate
- 29その他subjected to evaporation
- 30その他to remove the solvent
- 31洗浄the resulting colorless solid material was washed with an ether-hexane (2:1) mixture solution
実験手順
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.