BUTANAL, 2,2-DICHLORO-3-METHYL-

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture consisting of 1.55 g of 2,2-dichloroisovaleraldehyde, 1.27 g of benzaldehyde, and 8 ml of acetonitrile was cooled in an ice-water, and to the mixture was added 13.5 ml of concentrated aqueous ammonia, and then the resulting mixture was stirred for 66 hours at room temperature. The product was extracted with methylene chloride, and the extract was washed with water, dried over anhydrous magnesium sulfate, and evaporated to yield a crude product. The crude product was chromatographed using 30 g of silica gels, thereby contaminants which were eluted with 5% acetonitrile/methylene chloride were removed, and fractions which were eluted with 50% acetonitrile/methylene chloride were collected. The collected fractions were evaporated to yield 1.24 g of the residue, which was recrystallized from methylene chloride/ether to yield 0.947 g of crystals (yield: 51%). The product was extracted with methylene chloride the extract was washed with water dried over anhydrous magnesium sulfate evaporated to yield a crude product The crude product was chromatographed contaminants which were eluted with 5% acetonitrile/methylene chloride were removed fractions which were eluted with 50% acetonitrile/methylene chloride were collected The collected fractions were evaporated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: (2)In 970 ml of acetonitrile was dissolved 175 g (0.968 mol) of p-methoxybenzyloxyacetaldehyde (2d), followed by addition of 150 g (0.968 mol)of 2,2-dichloro-3-methylbutyraldehyde (1). Then, 1300 ml of 28% aqueous ammonia was further added dropwise under ice-cooling. After completion of dropwise addition, the mixture was allowed to stand at room temperature for 4 days. This reaction mixture was concentrated under reduced pressure and extracted with methylene chloride. The organic layer was washed with saturated brine and dried over MgSO4 and the solvent was distilled off under reduced pressure. The crude product was dissolved in ethyl acetate. To this solution was added a solution of oxalic acid (89.8 g, 0.968 mol)in ethyl acetate (70 ml)and the resulting oxalate was collected by filtration and rinsed with ethyl acetate. This oxalate was neutralized with 2N-sodium hydroxide and extracted with ethyl acetate. The organic layer was washed with water and dried over magnisium sulfate. The solvent was then distilled off under reduced pressure to provide 165 g (yield 69%)of 4-isopropyl-2-(p-methoxybenzyloxymethyl)-1H-imidazole (3d)as oil. cooling After completion of dropwise addition This reaction mixture was concentrated under reduced pressure extracted with methylene chloride The organic layer was washed with saturated brine dried over MgSO4 the solvent was distilled off under reduced pressure The crude product was dissolved in ethyl acetate the resulting oxalate was collected by filtration rinsed with ethyl acetate extracted with ethyl acetate The organic layer was washed with water dried over magnisium sulfate The solvent was then distilled off under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In 200 ml of acetonitrile was dissolved 53 g (339 mmol) of 2,2-dichloro-3-methylbutyraldehyde (1). Then, at 0° C., 45 g of benzyloxyacetaldehyde (2c)and 400 ml of aqueous ammonia (28%)were added. The mixture was stirred at room temperature for 15 hours. This reaction mixture was concentrated under reduced pressure and the residue was extracted with methylene chloride. The extract was washed with saturated brine, dried over sodium sulfate, and filtered. The filtrate was concentrated under reduced pressure to provide 2-(benzyloxymethyl)-4-isopropyl-1H-imidazole (3c). Yield 77 g (98.5%). This reaction mixture was concentrated under reduced pressure the residue was extracted with methylene chloride The extract was washed with saturated brine dried over sodium sulfate filtered The filtrate was concentrated under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture consisting of 1.55 g of 2,2-dichloroisovaleraldehyde, 1.27 g of benzaldehyde, and 8 ml of acetonitrile was cooled in an ice-water, and to the mixture was added 13.5 ml of concentrated aqueous ammonia, and then the resulting mixture was stirred for 66 hours at room temperature. The product was extracted with methylene chloride, and the extract was washed with water, dried over anhydrous magnesium sulfate, and evaporated to yield a crude product. The crude product was chromatographed using 30 g of silica gels, thereby contaminants which were eluted with 5% acetonitrile/methylene chloride were removed, and fractions which were eluted with 50% acetonitrile/methylene chloride were collected. The collected fractions were evaporated to yield 1.24 g of the residue, which was recrystallized from methylene chloride/ether to yield 0.947 g of crystals (yield: 51%). The product was extracted with methylene chloride the extract was washed with water dried over anhydrous magnesium sulfate evaporated to yield a crude product The crude product was chromatographed contaminants which were eluted with 5% acetonitrile/methylene chloride were removed fractions which were eluted with 50% acetonitrile/methylene chloride were collected The collected fractions were evaporated