反応 #4846

反応方程式

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

α,α-dichloromethyl methyl ether

hydrochloric acid

→

2-methoxy-4-[2,2,2-trifluoro-1-hydroxy-(trifluoromethyl)ethyl]benzaldehyde

収率 48.0%

溶媒

dichloromethane

—

ice

water

反応条件

後処理

1. 1
   workup.STIRRINGAfter the resulting solution is stirred for 15 minutes
2. 2
   workup.STIRRINGStirring
3. 3
   workup.ADDITIONThe solution is then added
4. 4
   その他The resulting organic phase is separated
5. 5
   その他leaving an aqueous phase which
6. 6
   洗浄is washed with three 300 ml portions of dichloromethane
7. 7
   洗浄The combined dichloromethane extracts are washed with 1N hydrochloric acid
8. 8
   乾燥The dichloromethane solution is dried with anhydrous magnesium sulfate
9. 9
   ろ過filtered
10. 10
    その他evaporated at reduced pressure
11. 11
    その他to obtain an oily solid which
12. 12
    その他is triturated with chlorobutane
13. 13
    ろ過filtered
14. 14
    その他recrystallized from chlorobutane

実験手順

To a solution of 31.6 g (0.12 mole) of 1-methoxy-3-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]benzene in 200 ml dichloromethane is added 38 g (0.2 mole) of titanium tetrachloride at 0°-5° with stirring under a nitrogen atmosphere. After the resulting solution is stirred for 15 minutes, 11.5 g (0.1 mole) of α,α-dichloromethyl methyl ether is added dropwise at 0°-5° C. Stirring is continued while the temperature of the solution is allowed to reach 20°-25° during 18 hours. The solution is then added with stirring to a solution of 100 ml 6N hydrochloric acid in 500 ml of ice and water. The resulting organic phase is separated leaving an aqueous phase which is washed with three 300 ml portions of dichloromethane. The combined dichloromethane extracts are washed with 1N hydrochloric acid and then with saturated sodium chloride solution. The dichloromethane solution is dried with anhydrous magnesium sulfate, filtered, and evaporated at reduced pressure to obtain an oily solid which is triturated with chlorobutane, filtered and recrystallized from chlorobutane to give 14.5 g of 2-methoxy-4-[2,2,2-trifluoro-1-hydroxy-(trifluoromethyl)ethyl]benzaldehyde having a melting point of 144°-146°.

出典