2-nitroethyl Acetate

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

実験手順: 64 g nitroethanol, 50 ml glacial acetic acid, 250 ml benzene and 5 drops conc. H2SO4 were refluxed, using a water separator for 8 hours; 12 ml of H2O were collected. The solution was evaporated and vacuum distilled (1 mm at 60° C) yielding 89 g colorless nitroethylacetate. for 8 hours 12 ml of H2O were collected The solution was evaporated vacuum distilled (1 mm at 60° C)

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

実験手順: To a solution of 6.8 grams (0.5m) of 4,4-dimercapto-3-buten-2-one in ethanol cooled to 10° C. was added 2.0 grams (0.5m) of sodium hydroxide dissolved in 30 ml of ethanol followed by dropwise addition at 0°-10° C. of 6.7 grams (0.5m) of nitroethylacetate dissolved in ethanol.

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

実験手順: To a solution of 6.8 grams (0.5m) of 4,4-dimercapto-3-buten-2-one in ethanol cooled to 10° C. was added 2.0 grams (0.5m) of sodium hydroxide dissolved in 30 ml of ethanol followed by dropwise addition at 0°-10° C. of 6.7 grams (0.5m) of nitroethylacetate dissolved in ethanol.

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

実験手順: A solution of methyl 1H-indole-4-carboxylate (7.34 g, 41.9 mmol), 2-nitroethyl acetate (6.90 g, 51.9 mmol) and 4-tert-butylcatechol (0.026 g, 0.16 mmol) in xylene (50 mL) was refluxed for 6 hrs. The solvent was evaporated under reduced pressure to give a residual dark oily raw product that was purified by short column chromatography on silica using ethyl acetate-light petroleum as eluent. The product was obtained as yellowish solid material in 79% yield. Mp: 103° C. MS m/z 249 [M+H]+. The solvent was evaporated under reduced pressure

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

実験手順: This compound was prepared according to M. E. Flaugh, T. A. Crowell, J. A. Clemens, B. D. Sawyer J. Med. Chem., 1979, 22, pp. 63-68. Acetic anhydride (8.06 g, 79.0 mmol) and NaOAc (1.45 g, 17.7 mmol) were mixed and heated. Two drops of pyridine were added. 2-nitroethanol (6.45 g, 70.8 mmol) was carefully added to the suspension at 30-35° C. during 30 min. Thereafter the mixture was stirred overnight at room temperature. The next morning the mixture contained undissolved NaOAc and a new orange precipitate. The reaction mixture was taken up between CHCl3 and water, washed 1× with water, 1× with brine and dried with MgSO4. Thereafter the solvent was evaporated under reduced pressure at 40° C. The remaining orange oil was co-evaporated first with chloroform and then five times with toluene and finally with chloroform to get the 6.90 g of pure compound. This compound was prepared heated washed 1× with water, 1× with brine dried with MgSO4 Thereafter the solvent was evaporated under reduced pressure at 40° C

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

実験手順: This compound was prepared according to M. E. Flaugh, T. A. Crowell, J. A. Clemens, B. D. Sawyer J. Med. Chem., 1979, 22, pp. 63-68. Acetic anhydride (8.06 g, 79.0 mmol) and NaOAc (1.45 g, 17.7 mmol) were mixed and heated. Two drops of pyridine were added. 2-nitroethanol (6.45 g, 70.8 mmol) was carefully added to the suspension at 30-35° C. during 30 min. Thereafter the mixture was stirred overnight at room temperature. The next morning the mixture contained undissolved NaOAc and a new orange precipitate. The reaction mixture was taken up between CHCl3 and water, washed 1× with water, 1× with brine and dried with MgSO4. Thereafter the solvent was evaporated under reduced pressure at 40° C. The remaining orange oil was co-evaporated first with chloroform and then five times with toluene and finally with chloroform to get the 6.90 g of pure compound. This compound was prepared heated washed 1× with water, 1× with brine dried with MgSO4 Thereafter the solvent was evaporated under reduced pressure at 40° C

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

実験手順: To 40 ml of absolute ethanol was added 1.38 g (0.060 gram atom) metallic sodium. When the reaction was completed, 10.2 g (0.060 mole) of 3-acetylmercaptocycloheptene in 20 ml of absolute ethanol was added and the reaction mixture was brought up to reflux for 15 minutes. The solution was then cooled to 0° and 7.98 g (0.060 mole) of 1-nitro-2-acetoxyethane in 20 ml absolute ethanol was added. The reaction was allowed to proceed for 3.0 hours at 0° and then was partitioned between 1 N HCl and methylene chloride. The aqueous phase was further extracted with methylene chloride. The organic phases were pooled, dried over sodium sulfate, and evaporated to afford 12 g (99%) of pure 3-[2-nitroethylthio]cycloheptene as a colorless oil. to reflux for 15 minutes The solution was then cooled to 0° was partitioned between 1 N HCl and methylene chloride The aqueous phase was further extracted with methylene chloride dried over sodium sulfate evaporated

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

実験手順: To 40 ml of absolute ethanol was added 1.38 g (.060 gram atom) metallic sodium. When the reaction was completed 10.2 g ( b .060 mole) of 3-acetylmercaptocycloheptane in 20 ml of absolute ethanol was added and the reaction mixture was brought up to reflux for 15 minutes. The solution was then cooled to 0° and 7.98 g (.060 mole) of 1-nitro-2-acetoxyethane in 20 ml absolute ethanol was added. The reaction was allowed to proceed for 3.0 hours at 0° and then was partitioned between lN HC1 and methylene chloride. The aqueous phase was further extracted with methylene chloride. The organic phases were pooled, dried over sodium sulfate, and evaporated to afford 12 g (99%) of pure 3-[2-nitroethylthio]cycloheptene as a colorless oil. was added to reflux for 15 minutes The solution was then cooled to 0° was partitioned between lN HC1 and methylene chloride The aqueous phase was further extracted with methylene chloride dried over sodium sulfate evaporated

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of nitroethyl acetate (1.80 g, 13.5 mmol), triethyl orthoformate (4.50 mL, 27.0 mmol) and acetic anhydride (3.57 mL, 37.8 mmol) was stirred at 120° C. for 1 hr, and then at 130° C. for 1 hr, and then at 140° C. for 2 hr. The reaction mixture was concentrated under reduced pressure, and ethanol (25 mL), ethyl sarcosinate hydrochloride (2.03 g, 13.2 mmol) and triethylamine (1.83 mL, 13.2 mmol) were added thereto. After stirring at room temperature for 30 min, a 20% ethanol solution (6.7 mL) of sodium ethoxide was added thereto, and the mixture was further stirred at 70° C. for 2 hr. The reaction mixture was concentrated under reduced pressure, the residue was acidified with 1N hydrochloric acid (100 mL), and the mixture was extracted with ethyl acetate (100 mL). The extract was washed with brine (50 mL), and dried over anhydrous sodium sulfate. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent, hexane:ethyl acetate=98:2→70:30) to give the title compound (981 mg, 35%) as a yellow solid. at 130° C. for 1 hr at 140° C. for 2 hr were added After stirring at room temperature for 30 min the mixture was further stirred at 70° C. for 2 hr The reaction mixture was concentrated under reduced pressure the mixture was extracted with ethyl acetate (100 mL) The extract was washed with brine (50 mL) dried over anhydrous sodium sulfate The insoluble material was removed by filtration the filtrate was concentrated under reduced pressure The residue was purified by silica gel column chromatography (eluent, hexane:ethyl acetate=98:2→70:30)

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

実験手順: 64 g nitroethanol, 50 ml glacial acetic acid, 250 ml benzene and 5 drops conc. H2SO4 were refluxed, using a water separator for 8 hours; 12 ml of H2O were collected. The solution was evaporated and vacuum distilled (1mm at 60° C) yielding 89 g colorless nitroethylacetate. for 8 hours 12 ml of H2O were collected The solution was evaporated vacuum distilled (1mm at 60° C)

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

実験手順: 64 g nitroethanol, 50 ml glacial acetic acid, 250 ml benzene and 5 drops conc. H2SO4 were refluxed, using a water separator for 8 hours; 12 ml of H2O were collected. The solution was evaporated and vacuum distilled (1 mm at 60° C) yielding 89 g colorless nitroethylacetate. for 8 hours 12 ml of H2O were collected The solution was evaporated vacuum distilled (1 mm at 60° C)

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

実験手順: 64 g nitroethanol, 50 ml glacial acetic acid, 250 ml benzene and 5 drops conc. H2SO4 were refluxed, using a water separator for 8 hours; 12 ml of H2O were collected. The solution was evaporated and vacuum distilled (1 mm at 60° C) yielding 89 g colorless nitroethylacetate. for 8 hours 12 ml of H2O were collected The solution was evaporated vacuum distilled (1 mm at 60° C)