2-methyl-1-(2,4,6-trihydroxyphenyl)propan-1-one

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under an atmosphere of nitrogen, 981 mg (5.00 mmol) of (2,4,6-trihydroxyphenyl) (2-propyl) ketone (4) was dissolved in 10.0 ml of dioxane, cooled with cold water at about 10° C., and stirred. Into the stirred solution, 554 ml (639 mg, 4.50 mmol, 0.900 equivalent) of boron trifluorideether complex was added by the use of a microsyringe. The resultant mixture was further stirred for 15 minutes and then a dioxane (9 ml) solution of 861 mg of 3-methyl-2-butenol was slowly added dropwise. After four hours, the reaction solution was poured into 100 ml of ether. The ether layer was washed sequentially with a saturated aqueous sodium hydrogen carbonate solution and saturated brine and dried over sodium sulfate. The produced solution was distilled under a reduced pressure to remove the solvent and obtain 1.76 g of a crude product in the form of a red viscous oily substance. The crude product was treated by silica gel column chromatography (50 g of Wako Gel C-300, and eluted sequentially with 200 ml each of petroleum ether:ether at varying ratios=9:1, 7:3, and 5:5) to isolate 417 mg of {3-(3-methyl-2-butenyl)-2,4,6-trihydroxyphenyl} (2-propyl) ketone (23) and 338 mg of 2,2-bis(3-methyl-2-butenyl)-3,5-dihydroxy-6-(2-methyl-1-oxopropyl) cyclohexa-3,5-dienone (13). The ether layer was washed sequentially with a saturated aqueous sodium hydrogen carbonate solution and saturated brine dried over sodium sulfate The produced solution was distilled under a reduced pressure to remove the solvent obtain 1.76 g of a crude product in the form of a red viscous oily substance eluted sequentially with 200 ml each of petroleum ether

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under an atmosphere of nitrogen, 600 mg (15.0 mmol, 3.00 equivalents) of an oily 60% sodium hydride was washed with dry hexane to remove paraffin. In this solution, 20 ml of dimethyl sulfoxide was placed and stirred at room temperature. To the resultant mixture, a dimethyl sulfoxide (5.0 ml) solution of 981 mg (5.00 mmol) of (2-propyl) (2,4,6-trihydroxyphenyl) ketone (4) was added over a period of 15 minutes and stirred for 30 minutes. Then, a dimethyl sulfoxide (5.0 ml) solution of 1.43 g (10.0 mmol, 2.00 equivalents) of 1-bromo-3-methyl-2-butene was added dropwise over a period of 30 minutes. The resultant mixture was stirred at room temperature for 14 hours. The mixture was poured into 50 ml of a cold 2 M hydrochloric acid solution and extracted from ether. The ether layer was washed with saturated brine, dried over sodium sulfate, and distilled to remove the solvent and obtain 1.580 g of a crude product in the form of red oily substance. The crude product was separated by silica gel column chromatography (65 g of Wako Gel C-200, benzene:ethyl acetate=9:1) into (a) 239 mg of a brown viscous oily substance, (b) 342 mg of an orange color viscous oily substance, and (c) 206 mg of a yellow crystalline substance sequentially in the order of elution as indexed by the thin layer chromatography. The fraction (a) was further purified by column chromatography (15 g of Wako Gel C-300, petroleum ether:ether=9:1) to obtain 58 mg of {3,5-bis(3-methyl-2-butenyl)-2,4,6-trihydroxyphenyl} (2-propyl) ketone (12) in the form of yellow crystals. Under an atmosphere of nitrogen, 600 mg (15.0 mmol, 3.00 equivalents) of an oily 60% sodium hydride was washed with dry hexane to remove paraffin stirred for 30 minutes extracted from ether The ether layer was washed with saturated brine dried over sodium sulfate distilled to remove the solvent obtain 1.580 g of a crude product in the form of red oily substance The crude product was separated by silica gel column chromatography (65 g of Wako Gel C-200, benzene:ethyl acetate=9:1) into (a) 239 mg of a brown viscous oily substance, (b) 342 mg of an orange color viscous oily substance, and (c) 206 mg of a yellow crystalline substance sequentially in the order of elution as indexed by the thin layer chromatography The fraction (a) was further purified by column chromatography (15 g of Wako Gel C-300, petroleum ether:ether=9:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a vessel fitted with a calcium chloride tube, 12.61 g (100.0 mmol) of 1,3,5-trihydroxybenzene (1) was suspended on a mixture of 35 ml of nitrobenzene and 45 ml of carbon disulfide and they were stirred. To the mixture, 40.0 g (300 mmol, 3.00 equivalents) of granular aluminum chloride was added piecemeal at room temperature. They were stirred for one hour and a nitrobenzene (10.0 ml) solution of 10.66 g (100.0 mmol, 1.000 equivalent) of isobutyryl chloride was slowly added dropwise to the mixture. After about 5 hours, the reaction mixture was poured into a cold 2 M hydrochloric acid (500 ml) solution to induce decomposition of aluminum salt and then was extracted from ether. The organic layer was washed with water and distilled off ether under a reduced pressure. To this was added a large amount of water and water was distilled under reduced pressure to remove nitrobenzene solvent by steam distillation method. The residue was dissolved in ether, washed with saturated brine, dried over sodium sulfate, and distilled under a reduced pressure to remove the solvent and obtain 21.7 g of a crude reaction product. By recrystallization of the crude product from petroleum ether-methylene chloride (1:1), 17.1 g (yield 87.2%) of the product (4) was obtained in the form of light yellow powdery crystals. In a vessel fitted with a calcium chloride tube They were stirred for one hour was extracted from ether The organic layer was washed with water distilled off ether under a reduced pressure To this was added a large amount of water and water was distilled under reduced pressure to remove nitrobenzene solvent by steam distillation method The residue was dissolved in ether washed with saturated brine dried over sodium sulfate distilled under a reduced pressure to remove the solvent obtain 21.7 g of a crude reaction product By recrystallization of the crude product from petroleum ether-methylene chloride (1:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a vessel fitted with a calcium chloride tube, 12.61 g (100.0 mmol) of 1,3,5-trihydroxybenzene (1) was suspended on a mixture of 35 ml of nitrobenzene and 45 ml of carbon disulfide and they were stirred. To the mixture, 40.0 g (300 mmol, 3.00 equivalents) of granular aluminum chloride was added piecemeal at room temperature. They were stirred for one hour and a nitrobenzene (10.0 ml) solution of 10.66 g (100.0 mmol, 1.000 equivalent) of isobutyryl chloride was slowly added dropwise to the mixture. After about 5 hours, the reaction mixture was poured into a cold 2 M hydrochloric acid (500 ml) solution to induce decomposition of aluminum salt and then was extracted from ether. The organic layer was washed with water and distilled off ether under a reduced pressure. To this was added a large amount of water and water was distilled under reduced pressure to remove nitrobenzene solvent by steam distillation method. The residue was dissolved in ether, washed with saturated brine, dried over sodium sulfate, and distilled under a reduced pressure to remove the solvent and obtain 21.7 g of a crude reaction product. By recrystallization of the crude product from petroleum ether-methylene chloride (1:1), 17.1 g (yield 87.2%) of the product (4) was obtained in the form of light yellow powdery crystals. In a vessel fitted with a calcium chloride tube They were stirred for one hour was extracted from ether The organic layer was washed with water distilled off ether under a reduced pressure To this was added a large amount of water and water was distilled under reduced pressure to remove nitrobenzene solvent by steam distillation method The residue was dissolved in ether washed with saturated brine dried over sodium sulfate distilled under a reduced pressure to remove the solvent obtain 21.7 g of a crude reaction product By recrystallization of the crude product from petroleum ether-methylene chloride (1:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under an atmosphere of nitrogen, 981 mg (5.00 mmol) of (2,4,6-trihydroxyphenyl) (2-propyl) ketone (4) was dissolved in 10.0 ml of dioxane, cooled with cold water at about 10° C., and stirred. Into the stirred solution, 554 ml (639 mg, 4.50 mmol, 0.900 equivalent) of boron trifluorideether complex was added by the use of a microsyringe. The resultant mixture was further stirred for 15 minutes and then a dioxane (9 ml) solution of 861 mg of 3-methyl-2-butenol was slowly added dropwise. After four hours, the reaction solution was poured into 100 ml of ether. The ether layer was washed sequentially with a saturated aqueous sodium hydrogen carbonate solution and saturated brine and dried over sodium sulfate. The produced solution was distilled under a reduced pressure to remove the solvent and obtain 1.76 g of a crude product in the form of a red viscous oily substance. The crude product was treated by silica gel column chromatography (50 g of Wako Gel C-300, and eluted sequentially with 200 ml each of petroleum ether:ether at varying ratios=9:1, 7:3, and 5:5) to isolate 417 mg of {3-(3-methyl-2-butenyl)-2,4,6-trihydroxyphenyl} (2-propyl) ketone (23) and 338 mg of 2,2-bis(3-methyl-2-butenyl)-3,5-dihydroxy-6-(2-methyl-1-oxopropyl) cyclohexa-3,5-dienone (13). The ether layer was washed sequentially with a saturated aqueous sodium hydrogen carbonate solution and saturated brine dried over sodium sulfate The produced solution was distilled under a reduced pressure to remove the solvent obtain 1.76 g of a crude product in the form of a red viscous oily substance eluted sequentially with 200 ml each of petroleum ether

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under an atmosphere of nitrogen, 600 mg (15.0 mmol, 3.00 equivalents) of an oily 60% sodium hydride was washed with dry hexane to remove paraffin. In this solution, 20 ml of dimethyl sulfoxide was placed and stirred at room temperature. To the resultant mixture, a dimethyl sulfoxide (5.0 ml) solution of 981 mg (5.00 mmol) of (2-propyl) (2,4,6-trihydroxyphenyl) ketone (4) was added over a period of 15 minutes and stirred for 30 minutes. Then, a dimethyl sulfoxide (5.0 ml) solution of 1.43 g (10.0 mmol, 2.00 equivalents) of 1-bromo-3-methyl-2-butene was added dropwise over a period of 30 minutes. The resultant mixture was stirred at room temperature for 14 hours. The mixture was poured into 50 ml of a cold 2 M hydrochloric acid solution and extracted from ether. The ether layer was washed with saturated brine, dried over sodium sulfate, and distilled to remove the solvent and obtain 1.580 g of a crude product in the form of red oily substance. The crude product was separated by silica gel column chromatography (65 g of Wako Gel C-200, benzene:ethyl acetate=9:1) into (a) 239 mg of a brown viscous oily substance, (b) 342 mg of an orange color viscous oily substance, and (c) 206 mg of a yellow crystalline substance sequentially in the order of elution as indexed by the thin layer chromatography. The fraction (a) was further purified by column chromatography (15 g of Wako Gel C-300, petroleum ether:ether=9:1) to obtain 58 mg of {3,5-bis(3-methyl-2-butenyl)-2,4,6-trihydroxyphenyl} (2-propyl) ketone (12) in the form of yellow crystals. Under an atmosphere of nitrogen, 600 mg (15.0 mmol, 3.00 equivalents) of an oily 60% sodium hydride was washed with dry hexane to remove paraffin stirred for 30 minutes extracted from ether The ether layer was washed with saturated brine dried over sodium sulfate distilled to remove the solvent obtain 1.580 g of a crude product in the form of red oily substance The crude product was separated by silica gel column chromatography (65 g of Wako Gel C-200, benzene:ethyl acetate=9:1) into (a) 239 mg of a brown viscous oily substance, (b) 342 mg of an orange color viscous oily substance, and (c) 206 mg of a yellow crystalline substance sequentially in the order of elution as indexed by the thin layer chromatography The fraction (a) was further purified by column chromatography (15 g of Wako Gel C-300, petroleum ether:ether=9:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a vessel fitted with a calcium chloride tube, 12.61 g (100.0 mmol) of 1,3,5-trihydroxybenzene (1) was suspended on a mixture of 35 ml of nitrobenzene and 45 ml of carbon disulfide and they were stirred. To the mixture, 40.0 g (300 mmol, 3.00 equivalents) of granular aluminum chloride was added piecemeal at room temperature. They were stirred for one hour and a nitrobenzene (10.0 ml) solution of 10.66 g (100.0 mmol, 1.000 equivalent) of isobutyryl chloride was slowly added dropwise to the mixture. After about 5 hours, the reaction mixture was poured into a cold 2 M hydrochloric acid (500 ml) solution to induce decomposition of aluminum salt and then was extracted from ether. The organic layer was washed with water and distilled off ether under a reduced pressure. To this was added a large amount of water and water was distilled under reduced pressure to remove nitrobenzene solvent by steam distillation method. The residue was dissolved in ether, washed with saturated brine, dried over sodium sulfate, and distilled under a reduced pressure to remove the solvent and obtain 21.7 g of a crude reaction product. By recrystallization of the crude product from petroleum ether-methylene chloride (1:1), 17.1 g (yield 87.2%) of the product (4) was obtained in the form of light yellow powdery crystals. In a vessel fitted with a calcium chloride tube They were stirred for one hour was extracted from ether The organic layer was washed with water distilled off ether under a reduced pressure To this was added a large amount of water and water was distilled under reduced pressure to remove nitrobenzene solvent by steam distillation method The residue was dissolved in ether washed with saturated brine dried over sodium sulfate distilled under a reduced pressure to remove the solvent obtain 21.7 g of a crude reaction product By recrystallization of the crude product from petroleum ether-methylene chloride (1:1)