methyl 4-(2-methoxy-2-oxoethyl)sulfanylbutanoate

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: To a suspension of sodium (3.5 g, 0.15 mol) in dry toluene (300 mL) was added an excess of methanol (30 mL). After sodium was disappeared, the excess methanol was removed as the methanol-toluene azeotrope. When the distillation temperature had reached 105° C., Methyl 4-{[2-(methyloxy)-2-oxoethyl]thio}butanoate (28.3 g, 0.14 mol) in toluene (90 mL) was added over a period of ten mins. The methanol-toluene azeotrope was removed by distillation, after the distillation temperature rose to 106° C., the reaction mixture was cooled to room temperature. The reaction mixture was poured into a mixture of ice (100 g) and 12N HCl (20 mL). The organic layer was removed and the aqueous layer was extracted with three 60 mL portions of ether and the combined organic layers were dried over Na2SO4. After removing the solvent, 23.4 g of crude product was obtained (Yield: 96%). the excess methanol was removed as the methanol-toluene azeotrope had reached 105° C. The methanol-toluene azeotrope was removed by distillation rose to 106° C. The reaction mixture was poured into a mixture of ice (100 g) and 12N HCl (20 mL) The organic layer was removed the aqueous layer was extracted with three 60 mL portions of ether the combined organic layers were dried over Na2SO4 After removing the solvent

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

実験手順: Sodium (3.5 g, 0.15 mol) was added to methanol (150 mL) carefully. After cooling to room temperature, methyl 2-mercaptoacetate (15.6 g, 0.13 mol) was added. The mixture was stirred for 30 mins at room temperature and a little of NaI and methyl 4-chlorobutanoate 20.0 g, 0.15 mol) were added. The reaction mixture was refluxed over night. After cooling to room temperature, the solvent was removed under reduced pressure, then the residue was dissolved in CH2Cl2 (100 mL). The solution was washed with H2O (30 mL), brine (30 mL), and dried with Na2SO4. After removing the solvent, 28.3 g of the crude product was obtained (Yield: 94%). The reaction mixture was refluxed over night After cooling to room temperature the solvent was removed under reduced pressure the residue was dissolved in CH2Cl2 (100 mL) The solution was washed with H2O (30 mL), brine (30 mL) dried with Na2SO4 After removing the solvent

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: To a suspension of sodium (3.5 g, 0.15 mol) in dry toluene (300 mL) was added an excess of methanol (30 mL). After sodium was disappeared, the excess methanol was removed as the methanol-toluene azeotrope. When the distillation temperature had reached 105° C., Methyl 4-{[2-(methyloxy)-2-oxoethyl]thio}butanoate (28.3 g, 0.14 mol) in toluene (90 mL) was added over a period of ten mins. The methanol-toluene azeotrope was removed by distillation, after the distillation temperature rose to 106° C., the reaction mixture was cooled to room temperature. The reaction mixture was poured into a mixture of ice (100 g) and 12N HCl (20 mL). The organic layer was removed and the aqueous layer was extracted with three 60 mL portions of ether and the combined organic layers were dried over Na2SO4. After removing the solvent, 23.4 g of crude product was obtained (Yield: 96%). the excess methanol was removed as the methanol-toluene azeotrope had reached 105° C. The methanol-toluene azeotrope was removed by distillation rose to 106° C. The reaction mixture was poured into a mixture of ice (100 g) and 12N HCl (20 mL) The organic layer was removed the aqueous layer was extracted with three 60 mL portions of ether the combined organic layers were dried over Na2SO4 After removing the solvent

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

実験手順: Sodium (3.5 g, 0.15 mol) was added to methanol (150 mL) carefully. After cooling to room temperature, methyl 2-mercaptoacetate (15.6 g, 0.13 mol) was added. The mixture was stirred for 30 mins at room temperature and a little of NaI and methyl 4-chlorobutanoate (20.0 g, 0.15 mol) were added. The reaction mixture was refluxed over night. After cooling to room temperature, the solvent was removed under reduced pressure, then the residue was dissolved in CH2Cl2 (100 mL). The solution was washed with H2O (30 mL), brine (30 mL), and dried with Na2SO4. After removing the solvent, 28.3 g of the crude product was obtained (Yield: 94%). The reaction mixture was refluxed over night After cooling to room temperature the solvent was removed under reduced pressure the residue was dissolved in CH2Cl2 (100 mL) The solution was washed with H2O (30 mL), brine (30 mL) dried with Na2SO4 After removing the solvent

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

実験手順: Sodium (3.5 g, 0.15 mol) was added to methanol (150 mL) carefully. After cooling to room temperature, methyl 2-mercaptoacetate (15.6 g, 0.13 mol) was added. The mixture was stirred for 30 mins at room temperature and a little of NaI and methyl 4-chlorobutanoate (20.0 g, 0.15 mol) were added. The reaction mixture was refluxed over night. After cooling to room temperature, the solvent was removed under reduced pressure, then the residue was dissolved in CH2Cl2 (100 mL). The solution was washed with H2O (30 mL), brine (30 mL), and dried with Na2SO4. After removing the solvent, 28.3 g of the crude product was obtained (Yield: 94%). The reaction mixture was refluxed over night After cooling to room temperature the solvent was removed under reduced pressure the residue was dissolved in CH2Cl2 (100 mL) The solution was washed with H2O (30 mL), brine (30 mL) dried with Na2SO4 After removing the solvent

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

実験手順: To a suspension of sodium (3.5 g, 0.15 mol) in dry toluene (300 mL) was added an excess of methanol (30 mL). After sodium was disappeared, the excess methanol was removed as the methanol-toluene azeotrope. When the distillation temperature had reached 105° C., Methyl 4-{[2-(methyloxy)-2-oxoethyl]thio}butanoate (28.3 g, 0.14 mol) in toluene (90 mL) was added over a period of ten mins. The methanol-toluene azeotrope was removed by distillation, after the distillation temperature rose to 106° C., the reaction mixture was cooled to room temperature. The reaction mixture was poured into a mixture of ice (100 g) and 12N HCl (20 mL). The organic layer was removed and the aqueous layer was extracted with three 60 mL portions of ether and the combined organic layers were dried over Na2SO4. After removing the solvent, 23.4 g of crude product was obtained (Yield: 96%). the excess methanol was removed as the methanol-toluene azeotrope had reached 105° C. The methanol-toluene azeotrope was removed by distillation rose to 106° C. The reaction mixture was poured into a mixture of ice (100 g) and 12N HCl (20 mL) The organic layer was removed the aqueous layer was extracted with three 60 mL portions of ether the combined organic layers were dried over Na2SO4 After removing the solvent

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

実験手順: Sodium (3.5 g, 0.15 mol) was added to methanol (150 mL) carefully. After cooling to room temperature, methyl 2-mercaptoacetate (15.6 g, 0.13 mol) was added. The mixture was stirred for 30 mins at room temperature and a little of NaI and methyl 4-chlorobutanoate 20.0 g, 0.15 mol) were added. The reaction mixture was refluxed over night. After cooling to room temperature, the solvent was removed under reduced pressure, then the residue was dissolved in CH2Cl2 (100 mL). The solution was washed with H2O (30 mL), brine (30 mL), and dried with Na2SO4. After removing the solvent, 28.3 g of the crude product was obtained (Yield: 94%). The reaction mixture was refluxed over night After cooling to room temperature the solvent was removed under reduced pressure the residue was dissolved in CH2Cl2 (100 mL) The solution was washed with H2O (30 mL), brine (30 mL) dried with Na2SO4 After removing the solvent

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

実験手順: Potassium t-butoxide (1 M in THF) (56.0 mL, 56.0 mmol) was added to an ice cold solution of methyl 4-[(2-methoxy-2-oxoethyl)sulfanyl]butanoate (10.5 g, 50.9 mmol) from (361a), in diethyl ether (200 mL) under nitrogen atmosphere. The reaction was allowed to warm to room temperature and stirred for 2 h. The reaction was partitioned between ethyl ether and water. The organic layer was washed with saturated aqueous sodium bicarbonate, dried over magnesium sulfate and concentrated to give methyl 3-oxotetrahydro-2H-thiopyran-2-carboxylate (8.5 g, 82%) as a yellow oil. The reaction was partitioned between ethyl ether and water The organic layer was washed with saturated aqueous sodium bicarbonate dried over magnesium sulfate concentrated

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

実験手順: Potassium t-butoxide (1 M in THF) (56.0 mL, 56.0 mmol) was added to an ice cold solution of methyl 4-[(2-methoxy-2-oxoethyl)sulfanyl]butanoate (10.5 g, 50.9 mmol) from (361a), in diethyl ether (200 mL) under nitrogen atmosphere. The reaction was allowed to warm to room temperature and stirred for 2 h. The reaction was partitioned between ethyl ether and water. The organic layer was washed with saturated aqueous sodium bicarbonate, dried over magnesium sulfate and concentrated to give methyl 3-oxotetrahydro-2H-thiopyran-2-carboxylate (8.5 g, 82%) as a yellow oil. The reaction was partitioned between ethyl ether and water The organic layer was washed with saturated aqueous sodium bicarbonate dried over magnesium sulfate concentrated

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

実験手順: Methyl thioglycolate (5.0 mL, 55.0 mmol) was added dropwise to an ice cold solution of sodium methoxide (55.0 mmol) in methanol (18 mL) over 15 minutes. Methyl bromobutyrate (9.9 g, 55.0 mmol) was added slowly. The reaction was allowed to warm to room temperature and stirred overnight. The resulting mixture was filtered, concentrated, and taken up in methylene chloride and filtered again. The filtrate was concentrated and the product was distilled to give methyl 4-[(2-methoxy-2-oxoethyl)sulfanyl]butanoate (6.34 g, 55%) as a clear oil. The resulting mixture was filtered concentrated filtered again The filtrate was concentrated the product was distilled