sodium;3-methylbutanoate

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a mixture of 2 ml of water and 2 ml of acetone is dissolved 0.26 g of sodium isovalerate, and 0.45 g of 16β-ethyl-17β-bromoacetoxy-4-estren-3-one and 10 ml of DMF are added to the above solution. The mixture is refluxed for 6 hours, and thereafter treated in the same manner as Example 26. The reaction mixture is then subjected to column chromatography. Following passage of 100 ml of diisopropyl ether-n-hexane (2:8), elution is carried out with 400 ml of a 1:1 mixture of the same solvents. The elutate is evaporated under reduced pressure to remove the solvent, giving 0.415 g of the above-identified compound as a colorless viscous oil. are added to the above solution The mixture is refluxed for 6 hours treated in the same manner as Example 26 passage of 100 ml of diisopropyl ether-n-hexane (2:8), elution is carried out with 400 ml of a 1:1 mixture of the same solvents The elutate is evaporated under reduced pressure to remove the solvent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a mixture of 2 ml of water and 2 ml of acetone is dissolved 0.26 g of sodium isovalerate, and 0.45 g of 16β-ethyl-17β-bromoacetoxy-4-estren-3-one and 10 ml of DMF are added to the above solution. The mixture is refluxed for 6 hours, and thereafter treated in the same manner as Example 26. The reaction mixture is then subjected to column chromatography. Following passage of 100 ml of diisopropyl ether-n-hexane (2:8), elution is carried out with 400 ml of a 1:1 mixture of the same solvents. The elutate is evaporated under reduced pressure to remove the solvent, giving 0.415 g of the above-identified compound as a colorless viscous oil. are added to the above solution The mixture is refluxed for 6 hours treated in the same manner as Example 26 passage of 100 ml of diisopropyl ether-n-hexane (2:8), elution is carried out with 400 ml of a 1:1 mixture of the same solvents The elutate is evaporated under reduced pressure to remove the solvent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 9.86 Grams of methyl acetoacetate were dissolved in 15 ml of water, and 12.67 g of a 30% aqueous sodium hydroxide solution was added thereto by drops while cooling the mixture to 25° C. or less. After having been stirred at 30°-35° C. for 3 hours, the mixture was adjusted to pH 7.0 with a concentrated aqueous hydrochloric acid solution. Thereafter, 1.07 g of sodium isovalerate and 2.42 g of tetrabutylammonium bromide were added thereto. Then a concentrated aqueous hydrochloric acid solution was added to the mixture so that the mixture had a pH of 6.8. Further, 26.2 g of a toluene solution containing 32.7% of 3-(2-methylphenylthio)propanal was added thereto and stirred at 45°-50° C. for 9 hours. The organic layer separated from the mixture was washed with a 5% aqueous acetic acid solution and then with a saturated aqueous sodium chloride solution. Thereafter the layer was dried over anhydrous magnesium sulfate. Removing the solvent from the layer under reduced pressure gave 10.32 g of crude 4-hydroxy-6-(2-methylphenylthio)-2-hexanone (purity: 67.8%, yield: 62.1%). A purified product was obtained by column chromatography. The purified product had an nD21 of 1.5660. by drops while cooling the mixture to 25° C. or less was added stirred at 45°-50° C. for 9 hours The organic layer separated from the mixture was washed with a 5% aqueous acetic acid solution Thereafter the layer was dried over anhydrous magnesium sulfate Removing the solvent from the layer under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 9.86 Grams of methyl acetoacetate were dissolved in 15 ml of water, and 12.67 g of a 30% aqueous sodium hydroxide solution was added thereto by drops while cooling the mixture to 25° C. or less. After having been stirred at 30°-35° C. for 3 hours, the mixture was adjusted to pH 7.0 with a concentrated aqueous hydrochloric acid solution. Thereafter, 1.07 g of sodium isovalerate and 2.42 g of tetrabutylammonium bromide were added thereto. Then a concentrated aqueous hydrochloric acid solution was added to the mixture so that the mixture had a pH of 6.8. Further, 26.2 g of a toluene solution containing 32.7% of 3-(2-methylphenylthio)propanal was added thereto and stirred at 45°-50° C. for 9 hours. The organic layer separated from the mixture was washed with a 5% aqueous acetic acid solution and then with a saturated aqueous sodium chloride solution. Thereafter the layer was dried over anhydrous magnesium sulfate. Removing the solvent from the layer under reduced pressure gave 10.32 g of crude 4-hydroxy-6-(2-methylphenylthio)-2-hexanone (purity: 67.8%, yield: 62.1%). A purified product was obtained by column chromatography. The purified product had an nD21 of 1.5660. by drops while cooling the mixture to 25° C. or less was added stirred at 45°-50° C. for 9 hours The organic layer separated from the mixture was washed with a 5% aqueous acetic acid solution Thereafter the layer was dried over anhydrous magnesium sulfate Removing the solvent from the layer under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 9.86 Grams of methyl acetoacetate were dissolved in 15 ml of water, and 12.67 g of a 30% aqueous sodium hydroxide solution was added thereto by drops while cooling the mixture to 25° C. or less. After having been stirred at 30°-35° C. for 3 hours, the mixture was adjusted to pH 7.0 with a concentrated aqueous hydrochloric acid solution. Thereafter, 1.07 g of sodium isovalerate and 2.42 g of tetrabutylammonium bromide were added thereto. Then a concentrated aqueous hydrochloric acid solution was added to the mixture so that the mixture had a pH of 6.8. Further, 26.2 g of a toluene solution containing 32.7% of 3-(2-methylphenylthio)propanal was added thereto and stirred at 45°-50° C. for 9 hours. The organic layer separated from the mixture was washed with a 5% aqueous acetic acid solution and then with a saturated aqueous sodium chloride solution. Thereafter the layer was dried over anhydrous magnesium sulfate. Removing the solvent from the layer under reduced pressure gave 10.32 g of crude 4-hydroxy-6-(2-methylphenylthio)-2-hexanone (purity: 67.8%, yield: 62.1%). A purified product was obtained by column chromatography. The purified product had an nD21 of 1.5660. by drops while cooling the mixture to 25° C. or less was added stirred at 45°-50° C. for 9 hours The organic layer separated from the mixture was washed with a 5% aqueous acetic acid solution Thereafter the layer was dried over anhydrous magnesium sulfate Removing the solvent from the layer under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 9.86 Grams of methyl acetoacetate were dissolved in 15 ml of water, and 12.67 g of a 30% aqueous sodium hydroxide solution was added thereto by drops while cooling the mixture to 25° C. or less. After having been stirred at 30°-35° C. for 3 hours, the mixture was adjusted to pH 7.0 with a concentrated aqueous hydrochloric acid solution. Thereafter, 1.07 g of sodium isovalerate and 2.42 g of tetrabutylammonium bromide were added thereto. Then a concentrated aqueous hydrochloric acid solution was added to the mixture so that the mixture had a pH of 6.8. Further, 26.2 g of a toluene solution containing 32.7% of 3-(2-methylphenylthio)propanal was added thereto and stirred at 45°-50° C. for 9 hours. The organic layer separated from the mixture was washed with a 5% aqueous acetic acid solution and then with a saturated aqueous sodium chloride solution. Thereafter the layer was dried over anhydrous magnesium sulfate. Removing the solvent from the layer under reduced pressure gave 10.32 g of crude 4-hydroxy-6-(2-methylphenylthio)-2-hexanone (purity: 67.8%, yield: 62.1%). A purified product was obtained by column chromatography. The purified product had an nD21 of 1.5660. by drops while cooling the mixture to 25° C. or less was added stirred at 45°-50° C. for 9 hours The organic layer separated from the mixture was washed with a 5% aqueous acetic acid solution Thereafter the layer was dried over anhydrous magnesium sulfate Removing the solvent from the layer under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a mixture of 2 ml of water and 2 ml of acetone is dissolved 0.26 g of sodium isovalerate, and 0.45 g of 16β-ethyl-17β-bromoacetoxy-4-estren-3-one and 10 ml of DMF are added to the above solution. The mixture is refluxed for 6 hours, and thereafter treated in the same manner as Example 26. The reaction mixture is then subjected to column chromatography. Following passage of 100 ml of diisopropyl ether-n-hexane (2:8), elution is carried out with 400 ml of a 1:1 mixture of the same solvents. The elutate is evaporated under reduced pressure to remove the solvent, giving 0.415 g of the above-identified compound as a colorless viscous oil. are added to the above solution The mixture is refluxed for 6 hours treated in the same manner as Example 26 passage of 100 ml of diisopropyl ether-n-hexane (2:8), elution is carried out with 400 ml of a 1:1 mixture of the same solvents The elutate is evaporated under reduced pressure to remove the solvent