반응 #4845

반응 방정식

3-bromo-1-methoxybenzene

1,2-dibromoethane

3-bromo-1-methoxybenzene

hexafluoroacetone

hexafluoroacetone

hexafluoroacetone

hydrochloric acid

magnesium

→

1-methoxy-3-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]benzene

용매

water

ether

tetrahydrofuran

water

tetrahydrofuran

반응 조건

후처리

1. 1
   온도cooled condenser
2. 2
   기타The resulting reaction mixture
3. 3
   온도heated gently until a reaction
4. 4
   기타To the stirred reaction mixture
5. 5
   온도that gentle reflux
6. 6
   온도is maintained
7. 7
   workup.STIRRINGThe reaction mixture is stirred for an additional two hours
8. 8
   온도The resulting solution is then cooled to 0°
9. 9
   기타the reaction flask is fitted with
10. 10
    기타topped by a dry ice condenser
11. 11
    workup.ADDITIONare added
12. 12
    workup.ADDITIONis added dropwise to the stirred solution which
13. 13
    온도is cooled to 0° to -10° with an ice-acetone bath
14. 14
    온도to warm to 20°-25°
15. 15
    workup.STIRRINGstirring
16. 16
    온도The solution is cooled to 0°
17. 17
    기타to obtain an acidic solution to which
18. 18
    세척The resulting ether layer is washed with water
19. 19
    세척washed with a 5% sodium bicarbonate solution
20. 20
    건조dried with anhydrous magnesium sulfate
21. 21
    여과filtered
22. 22
    기타evaporated at reduced pressure
23. 23
    기타to yield a residual solid which
24. 24
    기타is recrystallized from chlorobutane

실험 절차

To a suspension of 13.5 g (0.55 g atoms) of sublimed magnesium chips in 25 ml of anhydrous tetrahydrofuran in a reaction flask fitted with a water-cooled condenser are added 10 g (0.05 mole) of 3-bromo-1-methoxybenzene and 0.5 ml of 1,2-dibromoethane. The resulting reaction mixture is stirred and heated gently until a reaction is initiated. To the stirred reaction mixture is added dropwise a solution of 90 g (0.48 mole) of 3-bromo-1-methoxybenzene in 250 ml of anhydrous tetrahydrofuran at such a rate that gentle reflux is maintained. The reaction mixture is stirred for an additional two hours. The resulting solution is then cooled to 0° and the reaction flask is fitted with a jacketed dropping funnel topped by a dry ice condenser. The water condenser is replaced by an additional dry ice condenser. To the jacketed dropping funnel are added 85 g (50 ml) (0.55 mole) of condensed hexafluoroacetone. The condensed hexafluoroacetone is added dropwise to the stirred solution which is cooled to 0° to -10° with an ice-acetone bath. When the addition of the hexafluoroacetone is complete, the resulting solution is allowed to warm to 20°-25° and stirring is continued for an additional 18 hours. The solution is cooled to 0° and treated with 6N hydrochloric acid to obtain an acidic solution to which is added 1-liter of ether. The resulting ether layer is washed with water, washed with a 5% sodium bicarbonate solution, dried with anhydrous magnesium sulfate, filtered and evaporated at reduced pressure to yield a residual solid which is recrystallized from chlorobutane to give 78 g of 1-methoxy-3-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]benzene.

출처