Methyl trifluoromethyl ketone → 1,1,1-Trifluoro-2-methyl-3-(4-benzoylphenoxy)propan-2-ol

HRID 35879

Reaction equation

HRID 35879 reaction equation
[I-].C[S+](C)(C)=O.[OH-].[K+].[F:9][C:10]([F:15])([F:14])[C:11](=[O:13])[CH3:12].[OH:16][C:17]1[CH:30]=[CH:29][C:20]([C:21]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[O:22])=[CH:19][CH:18]=1.[OH-].[CH2:32]([N+](C)(C)C)C1C=CC=CC=1>ClCCl.O.O.C(O)C>[F:9][C:10]([F:15])([F:14])[C:11]([CH3:32])([OH:13])[CH2:12][O:16][C:17]1[CH:18]=[CH:19][C:20]([C:21](=[O:22])[C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[CH:29][CH:30]=1

Participants

9

Reactant 5

HCID 9871Methyl trifluoromethyl ketoneHCID 143474-HydroxybenzophenoneHCID 14797Potassium Hydroxide2×HCID 66854Benzyltrimethylammonium hydroxideHCID 74498Sulfoxonium, trimethyl-, iodide (1:1)

Product 1

HCID 199393221,1,1-Trifluoro-2-methyl-3-(4-benzoylphenoxy)propan-2-olYield 13.5%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 19096565Water ethanolSolvent

Conditions

Temperature
0 °C

Procedure

A suspension of trimethylsulfoxonium iodide (8.57 g, 38.9 mmol) in 50 mL of dichloromethane cooled to 0° C. was treated with a solution of KOH (2.18 g, 38.9 mmol) in water (40 ml). The ylide was treated with trifluoroacetone (4.36 g, 38.9 mmol) and the reaction was maintained at 0° C. for 0.5 hours followed by reflux for 1.5 hours. The reaction was cooled to 0° C. and treated with a solution of 4-Hydroxybenzophenone (7.72 g, 38.9 mmol), KOH (2.18 g, 38.9 mmol) in water/ethanol (40 ml/5 ml). The mixture was treated with N-benzyltrimethylammonium hydroxide (8.46 g, 50.6 mmol) and then refluxed for 18 hours. The mixture was poured into ice-water and extracted with dichloromethane. The combined extracts were dried and evaporated to yield a brown oil. Chromatography of this oil, eluting with dichloromethane/hexane/ethyl acetate provided the title compound as a white solid (1.7 g); mp 70° -73° C. NMR: 1.45 (s,3, CH3), 4.16 (q,2, CH2), 6.44 (s,1, OH), 7.16 (dd,2, J=7,2, Ar), 7.65 (m,7, Ar); MS: m/z=325(M+1). Analysis for C17H15F3O3 : Calculated: C, 62.96; H, 4.66; Found: C, 62.71: H, 4.61.

Workup

  1. temperaturethe reaction was maintained at 0° C. for 0.5 hours
  2. temperatureby reflux for 1.5 hours
  3. temperatureThe reaction was cooled to 0° C.
  4. temperaturerefluxed for 18 hours
  5. extractionextracted with dichloromethane
  6. customThe combined extracts were dried
  7. customevaporated
  8. customto yield a brown oil
  9. washChromatography of this oil, eluting with dichloromethane/hexane/ethyl acetate

Sources & evidence

ORD record
ord-cd40a8560c27481a861db48e1af3f320
Source dataset
uspto-grants-1995_05
Patent number
US05411973

Linked notes

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