thiolane

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:0.00; 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:; See reaction.notes.procedure_details.

実験手順: In a 100 ml three-necked flask, 3.5 g of tetrahydrothiophene was dissolved in 40 ml of acetone. To the solution, 6 g of 1-bromo-2-butanone was added dropwise while stirring. After leaving for 24 hours, the deposited white crystal was collected by filtration. The white crystal was ground to a powder, which was washed with ether. The powder was dried by a vacuum drier at 30° C. for six hours to obtain 6.86 g of 2-oxobutyl-thiacyclopentanium bromide (yield: 72.2%). After leaving for 24 hours the deposited white crystal was collected by filtration was washed with ether The powder was dried by a vacuum drier at 30° C. for six hours

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

実験手順: In 400 ml of acetonitrile was dissolved 53.2 g of tetrahydrothiophene, and to the solution was gradually added a solution containing 100 g of phenacyl bromide dissolved in 300 ml of acetonitrile. The solution was stirred at room temperature for 3 hours to deposit powder. The reaction solution was poured into 1,500 ml of ethyl acetate, and the powder deposited was collected by filtration and dried to obtain 137 g of phenacylthiophenium bromide. to the solution was gradually added a solution the powder deposited was collected by filtration dried

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

実験手順: In 100 ml of acetonitrile was dissolved 11.8 g of tetrahydrothiophene, to the solution was gradually added 20 g of 1-bromo-3,3-dimethyl-2-butanone. The mixture was stirred at room temperature for 2 days to deposit powder. After adding 100 ml of ethyl acetate to the reaction solution, the powder was collected by filtration, washed with ethyl acetate and dried to obtain 24 g of 2-oxo-3,3-dimethylbutyltetrahydrothiophenium bromide. the powder was collected by filtration washed with ethyl acetate dried

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a vigorously stirred solution of 10.0 grams (0.11 mole) of aniline in 200 ml. of methylene chloride cooled to -78° C. under nitrogen were added by means of a jacketed constant pressure additional funnel 11.7 grams (0.11 mole) of tert.-butyl hypochlorite also cooled to -78° C. This solution was stirred for 10 minutes. The funnel was rinsed with a few ml. of cold methylene chloride and 44 ml. (ca. 5 equivalents) of tetrahydrothiophene was cooled to -78° C., added dropwise to the reaction mixture, and stirred for three hours. In 50 ml. of methanol, 7.0 grams (0.13 mole, 1.2 equivalents) of sodium methoxide were placed in the funnel, cooled, and added quickly to the reaction mixture. The dry-ice/acetone cooling bath was removed and the solution stirred for 2 hours. The reaction was quenched by the addition of 100 ml. of water, the heterogeneous mixture separated, the aqueous layer was extracted two times with 100-ml. portions of methylene chloride. The combined organic layers were washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate, and filtered. The solvent was removed in vacuo to produce a dark red oil. Fractional distillation of the oil gave 5.03 grams (0.054 mole) of aniline and 6.11 grams (0.034 mole) of 2-(2-tetrahydrothienyl)aniline for a 31% yield based on starting material and a 64% yield based on unrecovered starting material: b.p. 130°-134° C. (0.19 mm), ND26.8 1.6258, IR (neat) 2.92, 3.36, 6.12, 6.70, and 13.40μ, NMR (CCl4)T 7.82 (4H, m), 6.99 (2H, m) 6.06 (2H, s), 5.52 (2H, t), 3.20 (4H, m). The funnel was rinsed with a few ml added dropwise to the reaction mixture stirred for three hours cooled added quickly to the reaction mixture The dry-ice/acetone cooling bath was removed the solution stirred for 2 hours The reaction was quenched by the addition of 100 ml of water, the heterogeneous mixture separated the aqueous layer was extracted two times with 100-ml The combined organic layers were washed with saturated sodium chloride solution dried over anhydrous sodium sulfate filtered The solvent was removed in vacuo to produce a dark red oil Fractional distillation of the oil

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a vigorously stirred solution of 10.0 grams (0.11 mole) of aniline in 200 ml. of methylene chloride cooled to -78° C. under nitrogen were added by means of a jacketed constant pressure additional funnel 11.7 grams (0.11 mole) of tert.-butyl hypochlorite also cooled to -78° C. This solution was stirred for 10 minutes. The funnel was rinsed with a few ml. of cold methylene chloride and 44 ml. (ca. 5 equivalents) of tetrahydrothiophene was cooled to -78° C., added dropwise to the reaction mixture, and stirred for three hours. In 50 ml. of methanol, 7.0 grams (0.13 mole, 1.2 equivalents) of sodium methoxide were placed in the funnel, cooled, and added quickly to the reaction mixture. The dry-ice/acetone cooling bath was removed and the solution stirred for 2 hours. The reaction was quenched by the addition of 100 ml. of water, the heterogeneous mixture separated, the aqueous layer was extracted two times with 100-ml. portions of methylene chloride. The combined organic layers were washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate, and filtered. The solvent was removed in vacuo to produce a dark red oil. Fractional distillation of the oil gave 5.03 grams (0.054 mole) of aniline and 6.11 grams (0.034 mole) of 2-(2-tetrahydrothienyl)aniline for a 31% yield based on starting material and a 64% yield based on unrecovered starting material: b.p. 130°-134° C. (0.19 mm), ND26.8 1.6258, IR (neat) 2.92, 3.36, 6.12, 6.70, and 13.40μ, NMR (CCl4)T 7.82 (4H, m), 6.99 (2H, m) 6.06 (2H, s), 5.52 (2H, t), 3.20 (4H, m). The funnel was rinsed with a few ml added dropwise to the reaction mixture stirred for three hours cooled added quickly to the reaction mixture The dry-ice/acetone cooling bath was removed the solution stirred for 2 hours The reaction was quenched by the addition of 100 ml of water, the heterogeneous mixture separated the aqueous layer was extracted two times with 100-ml The combined organic layers were washed with saturated sodium chloride solution dried over anhydrous sodium sulfate filtered The solvent was removed in vacuo to produce a dark red oil Fractional distillation of the oil