Methanol → HCID 54420183, compound

Participants

Reaction Steps

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.

Provenance & Evidence