反応 #217581

反応方程式

rac-2,2′-bis(diphenylphosphino)-1,1′-binapthyl

Cesium carbonate

4-bromo-2-nitroanisole

cis-2,6-dimethylpiperazine

→

title product ( D3 )

cis-3,5-Dimethyl-1-[4-(methyloxy)-3-nitrophenyl]piperazine

溶媒

dioxane

反応条件

後処理

1. 1
   温度the mixture heated
2. 2
   温度at reflux for 18 hours
3. 3
   ろ過The solids were filtered through celite
4. 4
   洗浄washed with ethyl acetate
5. 5
   濃縮The residue was concentrated
6. 6
   workup.DISSOLUTIONdissolved in ethyl acetate
7. 7
   抽出extracted with 2N hydrochloric acid (×5)
8. 8
   洗浄The combined extracts were washed in ethyl acetate (×3)
9. 9
   抽出extracted with dichloromethane (×5)
10. 10
    濃縮The combined organic extracts were concentrated
11. 11
    workup.DISSOLUTIONredissolved in ethyl acetate
12. 12
    洗浄washed with water (×3), saturated brine
13. 13
    乾燥dried over anhydrous sodium sulfate
14. 14
    濃縮concentrated
15. 15
    その他The residue was purified by column chromatography (Biotage Horizon, dichloromethane to 1:9 2M ammonia in methanol:dichloromethane)

実験手順

Palladium (II) acetate (941 mg, 4.2 mmol) and rac-2,2′-bis(diphenylphosphino)-1,1′-binapthyl (3.93 g, 6 mmol) were heated to 50° C. in dioxane (200 ml) for 30 minutes. Cesium carbonate (20.48 g, 63 mmol), 4-bromo-2-nitroanisole (9.75 g, 42 mmol) and cis-2,6-dimethylpiperazine (14.39 g, 126 mmol) were added and the mixture heated at reflux for 18 hours. The solids were filtered through celite and washed with ethyl acetate. The residue was concentrated and dissolved in ethyl acetate and extracted with 2N hydrochloric acid (×5). The combined extracts were washed in ethyl acetate (×3), basified with 0.880 ammonia and extracted with dichloromethane (×5). The combined organic extracts were concentrated, redissolved in ethyl acetate and washed with water (×3), saturated brine, dried over anhydrous sodium sulfate and concentrated. The residue was purified by column chromatography (Biotage Horizon, dichloromethane to 1:9 2M ammonia in methanol:dichloromethane) to afford the title product (D3). MS (ES+) m/e 266 [M+H]+.

出典