反応 #172407

反応方程式

hydrogen peroxide

9-borabicyclo[3.3.1]nonane

compound

1-(2,6-Dimethyl-4-nitrophenyl)-3-vinylpyridin-2(1H)-one

sodium hydroxide

→

1-(2,6-Dimethyl-4-nitrophenyl)-3-(2-hydroxyethyl)pyridin-2(1H)-one

溶媒

tetrahydrofuran

ethyl acetate

Water

反応条件

後処理

1. 1
   温度With ice-cooling
2. 2
   その他does not exceed 10-15° C
3. 3
   温度The mixture is then cooled and, at 0° C.-5° C.
4. 4
   workup.STIRRINGThe mixture is stirred briefly
5. 5
   その他does not exceed 30° C.
6. 6
   その他does not fall below 25° C
7. 7
   workup.ADDITIONAfter the addition
8. 8
   workup.STIRRINGthe mixture is stirred for another 30 min
9. 9
   その他After phase separation
10. 10
    抽出the aqueous phase is once more extracted with ethyl acetate
11. 11
    洗浄The combined organic phases are washed with an aqueous sodium bisulphite solution
12. 12
    その他The organic phase is removed
13. 13
    その他evaporated to dryness under reduced pressure
14. 14
    workup.DISSOLUTIONThe residue is dissolved in dichloromethane
15. 15
    その他purified by chromatography on silica gel (cyclohexane/ethyl acetate 1:2

実験手順

With ice-cooling, 1.15 l (575 mmol) of a 0.5 molar solution of 9-borabicyclo[3.3.1]nonane in tetrahydrofuran are added to 70.7 g (262 mmol) of the compound from Example 60A (alternative synthesis) such that the internal temperature does not exceed 10-15° C. The mixture is then warmed to RT and stirred at room temperature for 1.5 h. The mixture is then cooled and, at 0° C.-5° C., 653 ml (1.31 mol) of a 2-molar aqueous solution of sodium hydroxide are added. The mixture is stirred briefly, and 296 g (2.51 mol) of a 30% strength hydrogen peroxide solution are then added such that the temperature does not exceed 30° C. and does not fall below 25° C. After the addition has ended, the mixture is stirred for another 30 min. Water and ethyl acetate are added to the reaction mixture. After phase separation, the aqueous phase is once more extracted with ethyl acetate. The combined organic phases are washed with an aqueous sodium bisulphite solution. The organic phase is removed and evaporated to dryness under reduced pressure. The residue is dissolved in dichloromethane and purified by chromatography on silica gel (cyclohexane/ethyl acetate 1:2, then ethyl acetate). This gives 66.5 g (88% of theory) of the desired product.

出典