2,3-dimethyl-1-oxidopyridin-1-ium

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In methylene chloride (200 ml) was dissolved 2,3-dimethylpyridine (9.50 g) and the resulting solution was. cooled to 0° C. Metachloroperbenzoic acid (21.9 g) was added to the reaction mixture, followed by heating to room temperature. Stirring was conducted for 3 days. An aqueous solution of sodium sulfite was added and the resulting mixture was separated using methylene chloride (200 ml). The organic layer was dried over anhydrous magnesium sulfate, the filtrate was concentrated and the concentrate was purified by chromatography on a silica gel column (5% methanol—methylene chloride). Petroleum ether was added to the residue. Colorless powder so precipitated was collected by filtration, followed by drying, whereby the title compound (5.47 g) was obtained. by heating to room temperature the resulting mixture was separated The organic layer was dried over anhydrous magnesium sulfate the filtrate was concentrated the concentrate was purified by chromatography on a silica gel column (5% methanol—methylene chloride) Petroleum ether was added to the residue Colorless powder so precipitated was collected by filtration by drying

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Commercially available 2,3-lutidine (5.00 g) was dissolved in dichloromethane (50 ml) and the solution was cooled to 0° C. After that, the solution was added with meta-chloroperbenzoic acid (12.1 g) and then stirred at room temperature for 2 hours. After completion of the reaction, the solution was added with dichloromethane and washed with a 1 mol/l sodium hydroxide aqueous solution and saturated saline solution, followed by drying with anhydrous sodium sulfate. Then, the solvent was distilled off, thereby obtaining crude 2,3-lutidin-N-oxide (3.16 g). A 2.00 g part thereof was dissolved in dichloromethane (40 ml) and then the solution was cooled to 0° C. Subsequently, the solution was added with trifluoroacetic anhydride (4.49 ml), followed by stirring at room temperature for 4 hours and then at 45° C. for 3 hours. After completion of the reaction, the solvent was distilled off and the residue was dissolved in methanol (30 ml), followed by the addition of a sodium methoxide/methanol solution until the pH of the solution would reach pH=10. After the solution had been stirred at room temperature for 1 hour, the solvent was distilled off and extraction was then carried out with dichloromethane. The extract was dried with anhydrous sodium sulfate and the solvent was then distilled off, thereby obtaining 3-methyl-2-hydroxymethylpyridine (1.30 g). A 605.3 mg part thereof was dissolved in chloroform (30 ml) and then added with manganese dioxide (chemically processed product) (3.03 g), followed by stirring at 70° C. for 2 hours. After completion of the reaction, the catalyst was removed through Celite filtration and the solvent was then concentrated. Then, the residue was purified through silica gel column chromatography (chloroform/ethyl acetate), thereby obtaining the subject compound (419.8 mg) as a pale-orange colored liquid. After completion of the reaction washed with a 1 mol/l sodium hydroxide aqueous solution and saturated saline solution by drying with anhydrous sodium sulfate Then, the solvent was distilled off

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反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 71.79 g of 2,3-dimethylpyridine (II) was dissolved in 240 ml of acetic acid, to which 40 ml of 30% hydrogen peroxide solution was added and the resulting mixture was heated at 95° C. for 3 hours. Furthermore, 18 ml of a 30% hydrogen peroxide solution was added to the mixture and heated at 95° C. for 13 hours, and thereafter, 700 ml of water was added thereto and the resulting mixture was neutralized with sodium carbonate and extracted with chloroform. The resulting organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The resulting precipitation was recrystallized from diisopropylether to obtain 71.34 g of 2,3-dimethylpyridine N-oxide (III). was added heated at 95° C. for 13 hours extracted with chloroform The resulting organic layer was dried over anhydrous sodium sulfate the solvent was distilled off under reduced pressure The resulting precipitation was recrystallized from diisopropylether

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

実験手順: A solution of 183 mg of 2,3-dimethylpyridine 1-oxide in 0.6 ml of concentrated sulfuric acid was treated while cooling with ice with 0.2 ml of 65% nitric acid (d=1.4). The reaction mixture was stirred at 90° for 24 hours and poured on to a mixture of ice and sodium carbonate, whereupon the resulting mixture was extracted with methylene chloride and the methylene chloride phase was dried and evaporated. The residue, crystallized from ethanol/n-pentane, gave 2,3-dimethyl-4-nitropyridine 1-oxide of melting point 99°-102°. was extracted with methylene chloride the methylene chloride phase was dried evaporated The residue, crystallized from ethanol/n-pentane

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

実験手順: A solution of 15 g of 2,3-dimethylpyridine 1-oxide in 75 ml of chloroform was boiled at reflux and treated as rapidly as possible with 37 ml of trichloroacetyl chloride (the acid chloride was added through the reflux condenser). The reaction mixture was heated under reflux for 2.5 hours, subsequently poured into a mixture of ice and sodium bicarbonate and the resulting solution was washed several times with methylene chloride. The organic phase was dried with sodium sulfate, filtered and concentrated. The residue was chromatographed on silica gel with methylene chloride, the medium pressure flash chromatography method being used and the pressure being produced with nitrogen gas. The 2-chloromethyl-3-methylpyridine obtained was processed directly. at reflux was added through the reflux condenser) The reaction mixture was heated under reflux for 2.5 hours the resulting solution was washed several times with methylene chloride The organic phase was dried with sodium sulfate filtered concentrated The residue was chromatographed on silica gel with methylene chloride the pressure being produced with nitrogen gas

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

実験手順: A solution of 15 g of 2,3-dimethylpyridine 1-oxide in 75 ml of chloroform was boiled at reflux and treated as rapidly as possible with 37 ml of trichloroacetyl chloride (the acid chloride was added through the reflux condenser). The reaction mixture was heated under reflux for 2.5 hours, subsequently poured into a mixture of ice and sodium bicarbonate and the resulting solution was washed several times with methylene chloride. The organic phase was dried with sodium sulfate, filtered and concentrated. The residue was chromatographed on silica gel with methylene chloride, the medium pressure flash chromatography method being used and the pressure being produced with nitrogen gas. The 2-chloromethyl-3-methylpyridine obtained was processed directly. at reflux was added through the reflux condenser) The reaction mixture was heated under reflux for 2.5 hours the resulting solution was washed several times with methylene chloride The organic phase was dried with sodium sulfate filtered concentrated The residue was chromatographed on silica gel with methylene chloride the pressure being produced with nitrogen gas