反応 #325502

反応方程式

benzophenone imine

9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene

cesium carbonate

1-bromo-4,5-difluoro-2-propoxybenzene

ammonium chloride

→

4,5-difluoro-2-propoxyaniline

収率 38.2%

溶媒

toluene

toluene

water

反応条件

後処理

1. 1
   温度After the reaction mixture was cooled to room temperature
2. 2
   抽出The resulting mixture was extracted with ethyl acetate
3. 3
   乾燥The organic layer was dried over anhydrous magnesium sulfate
4. 4
   濃縮concentrated under reduced pressure
5. 5
   workup.DISSOLUTIONThe residue was dissolved with diethyl ether (60 ml), and concentrated hydrochloric acid (10 ml)
6. 6
   workup.ADDITIONwas added to the resulting solution, which
7. 7
   workup.STIRRINGwas then stirred for 2 hours
8. 8
   workup.ADDITIONA 5N sodium hydroxide aqueous solution (24 ml) was added to the reaction mixture
9. 9
   その他to get a pH=11
10. 10
    濃縮concentrated under reduced pressure
11. 11
    workup.DISSOLUTIONThe residue was dissolved in dichloromethane
12. 12
    洗浄washed with a saturated sodium chloride aqueous solution
13. 13
    濃縮The organic layer was concentrated under reduced pressure
14. 14
    その他The residue was then purified by silica gel column chromatography (n-hexane:ethyl acetate=9:1)
15. 15
    濃縮The purified product was concentrated under reduced pressure

実験手順

A toluene solution (20 ml) of benzophenone imine (2.38 g, 13.1 mmol), tris(dibenzylidene acetone)dipalladium (275 mg, 0.3 mmol), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (XANTPHOS) (347 mg, 0.6 mmol) and cesium carbonate (5.83 g, 17.9 mmol) were added to a toluene solution (60 ml) of 1-bromo-4,5-difluoro-2-propoxybenzene (3.0 g, 11.9 mmol). The mixture was stirred under a nitrogen atmosphere at 100° C. for 23 hours. After the reaction mixture was cooled to room temperature, water and a saturated ammonium chloride aqueous solution were added. The resulting mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The residue was dissolved with diethyl ether (60 ml), and concentrated hydrochloric acid (10 ml) was added to the resulting solution, which was then stirred for 2 hours. A 5N sodium hydroxide aqueous solution (24 ml) was added to the reaction mixture to get a pH=11, and concentrated under reduced pressure. The residue was dissolved in dichloromethane and washed with a saturated sodium chloride aqueous solution. The organic layer was concentrated under reduced pressure. The residue was then purified by silica gel column chromatography (n-hexane:ethyl acetate=9:1). The purified product was concentrated under reduced pressure to thereby obtain 850 mg of oily dark brown 4,5-difluoro-2-propoxyaniline (yield: 38%).

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