Hydrochloric Acid → 4-Hydroxy-6-(4-trifluoromethylphenylthio)2-hexanone

HRID 2373031Notes

Reaction equation

HRID 2373031 reaction equation
C(OC)(=O)[CH2:2][C:3]([CH3:5])=[O:4].[OH-].[Na+].Cl.C([O-])=O.[Na+].[F:16][C:17]([F:30])([F:29])[C:18]1[CH:23]=[CH:22][C:21]([S:24][CH2:25][CH2:26][CH:27]=[O:28])=[CH:20][CH:19]=1>O.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1>[OH:28][CH:27]([CH2:26][CH2:25][S:24][C:21]1[CH:22]=[CH:23][C:18]([C:17]([F:29])([F:16])[F:30])=[CH:19][CH:20]=1)[CH2:2][C:3](=[O:4])[CH3:5]

Participants

9

Reactant 5

HCID 313Hydrochloric Acid2×HCID 7757Methyl acetoacetateHCID 14798Sodium HydroxideHCID 2723810Sodium FormateHCID 143479823-(4-Trifluoromethylphenylthio)propanal

Product 1

HCID 145344724-Hydroxy-6-(4-trifluoromethylphenylthio)2-hexanoneYield 75.9%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

7.55 Grams of methyl acetoacetate were dissolved in 10 ml of water, and 9.1 g of a 30% aqueous sodium hydroxide solution were added thereto by drops while cooling the mixture to 35° C. or less. After having been stirred at 30°-35° C. for 3 hours, the mixture was adjusted to pH 7.5 with a concentrated aqueous hydrochloric acid solution. Thereafter, 0.35 g of sodium formate and 1.61 g of tetrabutylammonium bromide were added thereto and then 54.0 g of a toluene solution containing 17.4% of 3-(4-trifluoromethylphenylthio)propanal were added thereto. The mixture was stirred at 45°-50° C. for 10 hours and then at room temperature for 4 hours. After the mixture had been neutralized with a concentrated aqueous hydrochloric acid solution, the organic layer was separated, washed with a saturated aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate. Removing the solvent from the layer under reduced pressure gave 14.88 g of crude 4-hydroxy-6-(4-trifluoromethylphenylthio)2-hexanone (purity: 74.5%, yield: 75.9%).

Workup

  1. temperatureby drops while cooling the mixture to 35° C. or less
  2. additionwere added
  3. stirringThe mixture was stirred at 45°-50° C. for 10 hours
  4. waitat room temperature for 4 hours
  5. customthe organic layer was separated
  6. washwashed with a saturated aqueous sodium chloride solution
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customRemoving the solvent from the layer under reduced pressure

Sources & evidence

ORD record
ord-75cac6b259d544b5be59f8a9ea653a82
Source dataset
uspto-grants-1992_03
Patent number
US05101076

Reaction notes

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