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

HRID 35881

Reaction equation

HRID 35881 reaction equation
[OH-].[K+].[I-].[CH3:4][S+](C)(C)=O.[F:9][C:10]([F:15])([F:14])[C:11](=[O:13])[CH3:12].[C:16]1([S:22]([C:25]2[CH:30]=[CH:29][C:28]([SH:31])=[CH:27][CH:26]=2)(=[O:24])=[O:23])[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>O.ClCCl>[F:9][C:10]([F:15])([F:14])[C:11]([CH3:4])([OH:13])[CH2:12][S:31][C:28]1[CH:27]=[CH:26][C:25]([S:22]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)(=[O:24])=[O:23])=[CH:30][CH:29]=1

Participants

7

Reactant 4

HCID 9871Methyl trifluoromethyl ketoneHCID 14797Potassium Hydroxide2×HCID 74498Sulfoxonium, trimethyl-, iodide (1:1)HCID 129632484-(Phenylsulfonyl)benzenethiol

Product 1

HCID 199393061,1,1-Trifluoro-2-methyl-3-(4-phenylsulfonylphenylthio)propan-2-olYield 31.9%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent2×

Procedure

Potassium hydroxide (0.129 g, 2.3 mmol) in water (2 mL) was added dropwise to a stirred suspension of trimethylsulfoxonium iodide (0.476 g, 2.2 mmol), trifluoroacetone (0.258 g, 2.3 mmol) in dichloromethane (5 mL) under nitrogen at 0° C. The mixture was stirred for 0.5 hours and was then refluxed for a further 0.5 hour. After cooling to room temperature a solution of 4-(phenylsulfonyl)thiophenol (0.5 g, 2 mmol), potassium hydroxide (0.112 g, 2 mmol), and water (5 mL) was added in one portion and the mixture was stirred for 2 hours. The reaction mixture was diluted with dichloromethane, washed (saturated aqueous ammonium chloride solution, water, brine), and dried (Na2SO4). Evaporation gave an oil that crystallized from ether/ethyl acetate/hexane to give a white solid. The filtrate was evaporated to give a solid which was recrystallized from ether/hexane to give the title compound (0.24 g); mp 100°-102° C.; NMR: 1.35 (s,3 , CH3), 3.35 (m,2, SCH2), 6.41 (s,1, OH), 7.57 (d,2, J=9, Ar), 7.67 (m,3, Ar), 7.83 (d,2, J=8.7, Ar), 7.94 (d,2, J=6.9, Ar). MS: m/z=377 (M+1). Analysis for C16H15F3O3S2 : Calculated: C, 51.06; H, 4.02; Found: C, 51.50: H, 3.94.

Workup

  1. temperaturewas then refluxed for a further 0.5 hour
  2. additionwas added in one portion
  3. stirringthe mixture was stirred for 2 hours
  4. washwashed (saturated aqueous ammonium chloride solution, water, brine)
  5. dry with materialdried (Na2SO4)
  6. customEvaporation
  7. customgave an oil
  8. customthat crystallized from ether/ethyl acetate/hexane
  9. customto give a white solid
  10. customThe filtrate was evaporated
  11. customto give a solid which
  12. customwas recrystallized from ether/hexane

Sources & evidence

ORD record
ord-ac04449cb42d47dabe1b6c07f37eb93e
Source dataset
uspto-grants-1995_05
Patent number
US05411973

Linked notes

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