Methanol → HCID 54420183, compound

HRID 567210Notes

Reaction equation

HRID 567210 reaction equation
[H-].[Na+].CO.[CH3:5][CH:6]([CH3:19])[CH2:7][C:8]([C:10]1[C:15]([CH3:16])=[CH:14][C:13]([OH:17])=[CH:12][C:11]=1[OH:18])=[O:9].Cl[CH2:21][CH:22]=[C:23]([CH3:25])[CH3:24]>CCCCCC.CCOCC>[CH3:5][CH:6]([CH3:19])[CH2:7][C:8]([C:10]1[C:15]([CH3:16])=[CH:14][C:13]([O:17][CH2:21][CH:22]=[C:23]([CH3:25])[CH3:24])=[CH:12][C:11]=1[OH:18])=[O:9]

Participants

7

Reactant 4

HCID 887Methanol2×HCID 104291-Chloro-3-methyl-2-buteneHCID 24758Sodium hydrideHCID 54109422HCID 54109422, compound

Product 1

HCID 54420183HCID 54420183, compoundYield 7.8%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Procedure

Under an atmosphere of nitrogen, 300 mg (7.50 mmol, 1.50 equivalents) of an oil dispersion of 60% sodium hydride was washed with petroleum ether to remove paraffin and then combined with 7.5 ml of dry methanol. Then, a methanol (5.0 ml) solution of 1.04 g (5.00 mmol) of (2,4-dihydroxy-6-methylphenyl) (2-methylpropyl) ketone (47) was added cooling with ice and stirred. Further, a methanol (5.0 ml) solution of 784 mg (7.50 mmol, 1.50 equivalents) of 1-chloro-3-methyl-2-butene was slowly added dropwise. The resultant mixture was stirred at room temperature for two hours. The mixture was combined with ether. The ether layer was washed with a saturated aqueous ammonium chloride solution and saturated brine, dried over sodium sulfate, and distilled to remove the solvent and obtain 1.296 g of a dark red oily substance. This oily substance was combined with a small amount of hexane and left standing in a refrigerator to recover 277 mg of the starting substance in the form of colorless needle crystals. The filtrate, 965 mg in weight, was subjected to silica gel column chromatography (49 g of Wako Gel C-300, eluted with hexane:ethyl acetate at varying ratios=29 1-7:3) to produce sequentially by fractionation in the order of elution 108 mg of {2-hydroxy-6-methyl-4-(3-methyl-2-butenyloxy)phenyl} (2-methylpropyl) ketone (48) in the form of a yellow oily substance, 78 mg of {2,4-dihydroxy-6-methyl-3-(3-methyl-2-butenyl) phenyl} (2-methylpropyl) ketone (49) in the form of colorless fine crystals, and 260 mg of a yellowish brown oily substance which was again purified by column chromatography (6.0 g of Wako Gel C-300, eluted with hexane:ethyl acetate=19:1) to obtain 162 mg of {4,6-dihydroxy-2-methyl-3-(3-methyl-2-butenyl)phenyl} (3-methylpropyl) ketone (50) in the form of a yellow viscous oily substance.

Workup

  1. customto remove paraffin
  2. temperaturecooling with ice
  3. washThe ether layer was washed with a saturated aqueous ammonium chloride solution and saturated brine
  4. dry with materialdried over sodium sulfate
  5. distillationdistilled
  6. customto remove the solvent
  7. customobtain 1.296 g of a dark red oily substance
  8. waitleft
  9. customto recover 277 mg of the starting substance in the form of colorless needle crystals
  10. washThe filtrate, 965 mg in weight, was subjected to silica gel column chromatography (49 g of Wako Gel C-300, eluted with hexane:ethyl acetate at varying ratios=29 1-7:3)

Sources & evidence

ORD record
ord-5f21ccc1c47f402a968cae191662bc64
Source dataset
uspto-grants-2001_01
Patent number
US06177474B1

Reaction notes

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