1-Chloro-3-methyl-2-butene → HCID 53661470, compound

HRID 567213Notes

Reaction equation

HRID 567213 reaction equation
[OH:1][C:2]1[CH:7]=[C:6]([OH:8])[CH:5]=[CH:4][C:3]=1[C:9]([CH2:11][CH:12]([CH3:14])[CH3:13])=[O:10].Cl[CH2:16][CH:17]=[C:18]([CH3:20])[CH3:19].C[O-].[Na+]>CO>[CH3:13][CH:12]([CH3:14])[CH2:11][C:9]([C:3]1[CH:4]=[CH:5][C:6]([O:8][CH2:16][CH:17]=[C:18]([CH3:20])[CH3:19])=[CH:7][C:2]=1[OH:1])=[O:10].[CH3:13][CH:12]([CH3:14])[CH2:11][C:9]([C:3]1[CH:4]=[CH:5][C:6]([OH:8])=[C:7]([CH2:16][CH:17]=[C:18]([CH3:20])[CH3:19])[C:2]=1[OH:1])=[O:10]

Participants

6

Reactant 3

HCID 104291-Chloro-3-methyl-2-buteneHCID 8194681-(2,4-dihydroxyphenyl)-3-methylbutan-1-oneHCID 10942334Sodium Methoxide

Product 2

HCID 53661470HCID 53661470, compoundHCID 54531962HCID 54531962, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

Under an atmosphere of nitrogen, 486 mg (2.50 mmol) of (2,4-dihydroxyphenyl) (2-methylpropyl) ketone (52) and 784 mg (7.50 mmol, 3.00 equivalents) of 1-chloro-3-methyl-2-butene were dissolved in 7.0 ml of dry methanol. To the solution which was stirred at room temperature, a methanol (7.5 ml) solution of 405 mg (7.50 mmol, 3.00 equivalents) of sodium methoxide was slowly added dropwise. The resultant mixture was stirred at room temperature for three hours and then at 50° C. for one hour, and distilled at room temperature under a reduced pressure to remove methanol, and combined with ether. The ether layer was washed with a saturated aqueous ammonium chloride solution and saturated brine, dried over sodium sulfate, distilled off the solvent and obtain 661 mg of a red oily substance. The crude product was subjected to silica gel column chromatography (20 g of Wako Gel C-300, eluted with hexane:ether at varying ratios=50:1-4:1) to produce sequentially by fractionation in the order of elution 139 mg of {2-hydroxy-4-(3-methyl-2-butenyloxy)phenyl} (2-methylpropyl) ketone (53) in the form of a colorless oily substance and 41 mg of {2,4-dihydroxy-3-(3-methyl-2-butenyl)phenyl} (2-methylpropyl) ketone (54) in the form of colorless crystals.

Workup

  1. distillationdistilled at room temperature under a reduced pressure
  2. customto remove methanol
  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 off the solvent
  6. customobtain 661 mg of a red oily substance
  7. washThe crude product was subjected to silica gel column chromatography (20 g of Wako Gel C-300, eluted with hexane:ether at varying ratios=50:1-4:1)

Sources & evidence

ORD record
ord-867c7234bf774b7dab10c4fc32b13d2a
Source dataset
uspto-grants-2001_01
Patent number
US06177474B1

Reaction notes

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