Acetic Acid → Benzyl 4-(2,2-difluorovinyloxy)phenyl ketone

HRID 477433Notes

Reaction equation

HRID 477433 reaction equation
C([Li])CCC.C(NC(C)C)(C)C.[F:13][C:14](F)([F:32])[CH2:15][O:16][C:17]1[CH:22]=[CH:21][C:20]([C:23]([CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)=[O:24])=[CH:19][CH:18]=1.C(O)(=O)C>CCCCCC.O1CCCC1>[F:13][C:14]([F:32])=[CH:15][O:16][C:17]1[CH:18]=[CH:19][C:20]([C:23]([CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)=[O:24])=[CH:21][CH:22]=1

Participants

7

Conditions

Temperature
0 °C

Procedure

Butyllithium (190 ml; 1.6N) in hexane was added, dropwise, to diisopropylamine (30.4 g; 0.3 mol) in tetrahydrofuran (400 ml) kept under nitrogen at 0° C. The mixture was stirred for 30 minutes at 0° C. and then cooled to -70° C. At this temperature benzyl 4-(2,2,2-trifluoroethoxy)phenyl ketone, dissolved in tetrahydrofuran (70 ml) was slowly added, dropwise, to the reaction mixture. The solution became deep red. The mixture was then stirred at -70° C. for an hour and acetic acid (20 ml) was added, dropwise, without allowing the temperature of the reaction mixture to rise above -65° C. The mixture was then warmed to room temperature and added to ice-water (2000 ml). It was extracted with diethyl ether (3×500 ml) and the purified organic phase washed with sodium hydrogen carbonate, dried over magnesium sulphate and concentrated in a rotary evaporator. The residue was recrystallised from ethanol to give pure benzyl 4-(2,2-difluorovinyloxy)phenyl ketone.

Workup

  1. customkept under nitrogen at 0° C
  2. temperaturecooled to -70° C
  3. additionwas slowly added
  4. stirringThe mixture was then stirred at -70° C. for an hour
  5. customto rise above -65° C
  6. temperatureThe mixture was then warmed to room temperature
  7. extractionIt was extracted with diethyl ether (3×500 ml)
  8. washthe purified organic phase washed with sodium hydrogen carbonate
  9. dry with materialdried over magnesium sulphate
  10. concentrationconcentrated in a rotary evaporator
  11. customThe residue was recrystallised from ethanol

Sources & evidence

ORD record
ord-4750a94f93504a98841f53d9de765b37
Source dataset
uspto-grants-1989_12
Patent number
US04888340

Reaction notes

Loading…