3-chlorobutanoyl chloride

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

実験手順: In 25 ml of methylene chloride was suspended 13.3 g of anhydrous aluminum chloride, and 7.3 g of 3-chloro-3-methylpropionyl chloride was added to the suspension with ice-cooling, after which 8.2 g of 3-benzylpyridine hydrochloride was added in small portions to the suspension. The resulting mixture was subjected to reaction with ice-cooling for 2 hours and then at room temperature for one hour. The reaction mixture was added in small portions to a mixture of 246 ml of iced water and 49 ml of methylene chloride, and the organic layer was separated, while the aqueous layer was extracted with 40 ml of methylene chloride. The organic layers were combined and then 80 ml of water was added thereto after which the resulting mixture was neutralized with sodium hydrogencarbonate. The organic layer was separated, washed with 50 ml of water, and thereafter dried over anhydrous magnesium sulfate. The solvent was removed by distillation under reduced pressure, and the residue thus obtained was purified by a column chromatography [Wako Silica Gel C-200, eluant: chloroform:ethyl acetate (1:1 by volume)] to obtain 10.53 g (yield 96.0%) of colorless, oily 3-[p-(3-chloro-2-methylpropionyl)benzyl]pyridine. was added to the suspension with ice- cooling The resulting mixture was subjected to reaction with ice- cooling for 2 hours the organic layer was separated, while the aqueous layer was extracted with 40 ml of methylene chloride 80 ml of water was added The organic layer was separated washed with 50 ml of water dried over anhydrous magnesium sulfate The solvent was removed by distillation under reduced pressure the residue thus obtained was purified by a column chromatography [Wako Silica Gel C-200, eluant: chloroform:ethyl acetate (1:1 by volume)]

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

実験手順: 1,2,3,4-tetrahydro-2-methyl-6-nitrobenzofuro[3,2-c]pyridine (0.0224 mol), prepared according to the procedure described in J. Chem. Soc. (C), 1971, p53-60, was dissolved in 1,2-dichloroethane (40 ml), and cooled to 0° C. At this temperature, (1-chloroethyl) acetylchloride (0.0291 mol) was added dropwise. The suspension was stirred and refluxed for 2 hours. 1,2-dichloroethane was evaporated. The mixture was dissolved in methanol, stirred and refluxed for 2 hours, then filtered. Both the filtrate and crystals were treated with 2 N Na2CO3 and this mixture was extracted with CH2Cl2. The separated organic layer was dried, filtered, and the solvent evaporated. The residue was purified by column chromatography over silica gel (eluent: CH2Cl2 /CH3OH 90/10). The desired fractions were collected and the solvent was evaporated, yielding 1.5 g 1,2,3,4-tetrahydro-6-nitrobenzofuro[3,2-c]-pyridine (intern. 4). refluxed for 2 hours 1,2-dichloroethane was evaporated The mixture was dissolved in methanol stirred refluxed for 2 hours filtered Both the filtrate and crystals were treated with 2 N Na2CO3 this mixture was extracted with CH2Cl2 The separated organic layer was dried filtered the solvent evaporated The residue was purified by column chromatography over silica gel (eluent: CH2Cl2 /CH3OH 90/10) The desired fractions were collected the solvent was evaporated

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

実験手順: In 25 ml of methylene chloride was suspended 13.3 g of anhydrous aluminum chloride, and 7.3 g of 3-chloro-3-methylpropionyl chloride was added to the suspension with ice-cooling, after which 8.2 g of 3-benzylpyridine hydrochloride was added in small portions to the suspension. The resulting mixture was subjected to reaction with ice-cooling for 2 hours and then at room temperature for one hour. The reaction mixture was added in small portions to a mixture of 246 ml of iced water and 49 ml of methylene chloride, and the organic layer was separated, while the aqueous layer was extracted with 40 ml of methylene chloride. The organic layers were combined and then 80 ml of water was added thereto after which the resulting mixture was neutralized with sodium hydrogencarbonate. The organic layer was separated, washed with 50 ml of water, and thereafter dried over anhydrous magnesium sulfate. The solvent was removed by distillation under reduced pressure, and the residue thus obtained was purified by a column chromatography [Wako Silica Gel C-200, eluant: chloroform:ethyl acetate (1:1 by volume)] to obtain 10.53 g (yield 96.0%) of colorless, oily 3-[p-(3-chloro-2-methylpropionyl)benzyl]pyridine. was added to the suspension with ice- cooling The resulting mixture was subjected to reaction with ice- cooling for 2 hours the organic layer was separated, while the aqueous layer was extracted with 40 ml of methylene chloride 80 ml of water was added The organic layer was separated washed with 50 ml of water dried over anhydrous magnesium sulfate The solvent was removed by distillation under reduced pressure the residue thus obtained was purified by a column chromatography [Wako Silica Gel C-200, eluant: chloroform:ethyl acetate (1:1 by volume)]