Ethanol → 6-(4-Hydroxy-3,5-diisopropyl-phenyl)-hexanoic acid ethyl ester

HRID 2289680Notes

Reaction equation

HRID 2289680 reaction equation
B(F)(F)F.CCOCC.[CH2:10]([O:12][C:13](=[O:33])[CH2:14][CH2:15][CH2:16][CH2:17][C:18]([C:20]1[CH:25]=[C:24]([CH:26]([CH3:28])[CH3:27])[C:23]([OH:29])=[C:22]([CH:30]([CH3:32])[CH3:31])[CH:21]=1)=O)[CH3:11].C(S)(S)C.C(O)C>ClCCl.[Ni].O>[CH2:10]([O:12][C:13](=[O:33])[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][C:20]1[CH:21]=[C:22]([CH:30]([CH3:32])[CH3:31])[C:23]([OH:29])=[C:24]([CH:26]([CH3:28])[CH3:27])[CH:25]=1)[CH3:11]

Participants

8

Reactant 4

HCID 702EthanolHCID 8000Boron trifluoride etherate2×HCID 336451,1-EthanedithiolHCID 537233496-(4-Hydroxy-3,5-diisopropyl-phenyl)-6-oxo-hexanoic acid ethyl ester

Product 1

HCID 539382746-(4-Hydroxy-3,5-diisopropyl-phenyl)-hexanoic acid ethyl ester

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

Boron trifluoride diethyl etherate (4.8 mL, 39 mmol) was added to a mixture of 6-(4-hydroxy-3,5-diisopropyl-phenyl)-6-oxo-hexanoic acid ethyl ester (13.19 g, 39.4 mmol) and ethanedithiol (3.5 mL, 39.3 mmol) in dichloromethane (100 mL), and the resulting deep red mixture was stirred overnight at room temperature. An additional amount of boron trifluoride diethyl etherate (1.2 mL, 10 mmol) was added, and the reaction mixture was stirred an additional 4 hours at room temperature. The reaction mixture was washed with saturated aqueous sodium bicarbonate solution, and the organic solution was dried over magnesium sulfate, filtered, and concentrated to an orange oil. The oil was chromatographed on silica gel (70-230 mesh) using 19:1, then 9:1, then 83:17 hexanes/ethyl acetate, v/v, as eluant. A mixture of this dithioketal (3.65 g, 8.9 mmol), Raney nickel (41 g of a slurry in water), and ethanol (250 mL) is heated to 50° C. for 2.5 hours under nitrogen. No starting material remained by tlc. The ethanol was decanted from the nickel and the nickel washed and decanted twice with ethanol. The combined ethanol solutions were passed through celite, the ethanol evaporated, and the residue chromatographed on silica gel (70 230 mesh) using 4:1, hexanes/ethyl acetate as eluant. The product was obtained as a yellow oil in two portions, 2.95 g. CI Mass Spectrum: [M+H+ ]+ =320.

Workup

  1. stirringthe reaction mixture was stirred an additional 4 hours at room temperature
  2. washThe reaction mixture was washed with saturated aqueous sodium bicarbonate solution
  3. dry with materialthe organic solution was dried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated to an orange oil
  6. customThe oil was chromatographed on silica gel (70-230 mesh)
  7. temperatureis heated to 50° C. for 2.5 hours under nitrogen
  8. customThe ethanol was decanted from the nickel
  9. washthe nickel washed
  10. customdecanted twice with ethanol
  11. customthe ethanol evaporated
  12. customthe residue chromatographed on silica gel (70 230 mesh)
  13. customThe product was obtained as a yellow oil in two portions, 2.95 g

Sources & evidence

ORD record
ord-78bf1b14b750404198a9fb0102931a31
Source dataset
uspto-grants-2000_07
Patent number
US06093744

Reaction notes

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