Reaction #172407

Reaction equation

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

Solvents

tetrahydrofuran

ethyl acetate

Water

Conditions

Workup

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

Procedure

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.

Source