ethyl 3-sulfanylpropanoate

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: To a stirred solution of 1,3-dichloroacetone (6.85 g, 54 mmol) and ethyl 3-mercaptopropionate (13.9 mL, 108 mmol) in anhydrous tetrahydrofuran (150 mL) was dropwise added triethylamine (15.0 mL, 108 mmol) at 0° C. and stirred at room temperature for 24 h. The solvent was evaporated and the residue was partitioned between water and ethyl acetate. The ethyl acetate phase was washed with 5% hydrochloric acid and then brine, dried over sodium sulfate, and concentrated to dryness, affording 17.4 g of the crude 1,3-bis(2-ethoxycarbonylethylthio)acetone. at 0° C. The solvent was evaporated the residue was partitioned between water and ethyl acetate The ethyl acetate phase was washed with 5% hydrochloric acid brine, dried over sodium sulfate concentrated to dryness

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

Procedure: To a stirred solution of 1,3-dichloroacetone (6.85 g, 54 mmol) and ethyl 3-mercaptopropionate (13.9 mL, 108 mmol) in anhydrous tetrahydrofuran (150 mL) was dropwise added triethylamine (15.0 mL, 108 mmol) at 0° C. and stirred at room temperature for 24 h. The solvent was evaporated and the residue was partitioned between water and ethyl acetate. The ethyl acetate phase was washed with 5% hydrochloric acid and then brine, dried over sodium sulfate, and concentrated to dryness, affording 17.4 g of the crude 1,3-bis(2-ethoxycarbonylethylthio)acetone. at 0° C. The solvent was evaporated the residue was partitioned between water and ethyl acetate The ethyl acetate phase was washed with 5% hydrochloric acid brine, dried over sodium sulfate concentrated to dryness

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

Procedure: To a stirred solution of 1,3-dichloroacetone (6.85 g, 54 mmol) and ethyl 3-mercaptopropionate (13.9 mL, 108 mmol) in anhydrous tetrahydrofuran (150 mL) was dropwise added triethylamine (15.0 mL, 108 mmol) at 0° C. and stirred at room temperature for 24 h. The solvent was evaporated and the residue was partitioned between water and ethyl acetate. The ethyl acetate phase was washed with 5% hydrochloric acid and then brine, dried over sodium sulfate, and concentrated to dryness, affording 17.4 g of the crude 1,3-bis(2-ethoxycarbonylethylthio)acetone. at 0° C. The solvent was evaporated the residue was partitioned between water and ethyl acetate The ethyl acetate phase was washed with 5% hydrochloric acid brine, dried over sodium sulfate concentrated to dryness

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

Procedure: 1-Bromopentadecane is reacted in the usual way with ethyl β-mercaptopropionate and the syrup obtained reduced with lithium aluminium hydride to give a yield of 84% of theory of 3-pentadecylthiopropanol; m.p. 36°-39° C. the syrup obtained

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl 3-mercaptopropionate (22.46 g) was dissolved in absolute ethanol (60 mL) and the solution was cooled to -20° C. To it was added sodium ethoxide solution in ethanol (62.5 mL of 21%). A solution of ethyl 2-bromoisovalerate (35 g) in absolute ethanol (60 mL) was added slowly. The reaction mixture was stirred for 2 hours while the reaction temperature was allowed to warm to room temperature. Saturated NH4Cl (150 mL) was added to the reaction mixture and organic layer was separated. The aqueous layer was extracted with ethyl acetate (100 mL×3). The combined organic layers were dried over Na2SO4 and concentrated. Sodium (0.88 g) was dissolved in absolute ethanol (40 mL) at 0° C. and the solution was concentrated. The residue was dissolved in toluene and the product from the previous reaction, Compound 10, (7.78 g) was added. The reaction mixture was heated to reflux for 2 hours. The reaction mixture was cooled to room temperature and 1N HCl was added to the reaction mixture until the pH became acidic. The crude product was extracted with EtOAc (50 mL×3) and the combined organic layers were washed with brine, were dried over Na2SO4 and concentrated. The residue, Compound 11, was heated with 10% H2SO4 (40 mL) at 100° C. overnight. The crude product was extracted with ethyl acetate (50 mL×3). The combined organic layers were dried over Na2SO4 and concentrated. The residue (2(S,R)-(methylethyl)-tetrahydrothiophen-3-one), compound 12, was dissolved in methylene chloride (60 mL) and the solution was cooled to 0° C. Diisobutylaluminumhydride (25 mL, 1M) in methylene chloride was added dropwise. The reaction mixture was stirred for one hour at 0° C. The reaction was quenched by the dropwise addition of water until no gas evolved. 1N HCl (50 mL) was added and the crude product was extracted with methylene chloride (50 mL×3). Combined organic layers were washed with saturated NaHCO3, brine and dried over Na2SO4. Concentration and purification by column chromatography, eluting with 20% ethyl acetate in hexane gave Compound 13, as an oil (1.72 g): to warm to room temperature was separated The aqueous layer was extracted with ethyl acetate (100 mL×3) The combined organic layers were dried over Na2SO4 concentrated Sodium (0.88 g) was dissolved in absolute ethanol (40 mL) at 0° C. the solution was concentrated The residue was dissolved in toluene the product from the previous reaction, Compound 10, (7.78 g) was added The reaction mixture was heated to reflux for 2 hours The reaction mixture was cooled to room temperature The crude product was extracted with EtOAc (50 mL×3) the combined organic layers were washed with brine were dried over Na2SO4 concentrated The residue, Compound 11, was heated with 10% H2SO4 (40 mL) at 100° C. overnight The crude product was extracted with ethyl acetate (50 mL×3) The combined organic layers were dried over Na2SO4 concentrated The residue (2(S,R)-(methylethyl)-tetrahydrothiophen-3-one), compound 12, was dissolved in methylene chloride (60 mL) the solution was cooled to 0° C Diisobutylaluminumhydride (25 mL, 1M) in methylene chloride was added dropwise The reaction mixture was stirred for one hour at 0° C The reaction was quenched by the dropwise addition of water until no gas 1N HCl (50 mL) was added the crude product was extracted with methylene chloride (50 mL×3) Combined organic layers were washed with saturated NaHCO3, brine dried over Na2SO4 Concentration and purification by column chromatography eluting with 20% ethyl acetate in hexane

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl 3-mercaptopropionate (22.46 g) was dissolved in absolute ethanol (60 mL) and the solution was cooled to -20° C. To it was added sodium ethoxide solution in ethanol (62.5 mL of 21%). A solution of ethyl 2-bromoisovalerate (35 g) in absolute ethanol (60 mL) was added slowly. The reaction mixture was stirred for 2 hours while the reaction temperature was allowed to warm to room temperature. Saturated NH4Cl (150 mL) was added to the reaction mixture and organic layer was separated. The aqueous layer was extracted with ethyl acetate (100 mL×3). The combined organic layers were dried over Na2SO4 and concentrated. Sodium (0.88 g) was dissolved in absolute ethanol (40 mL) at 0° C. and the solution was concentrated. The residue was dissolved in toluene and the product from the previous reaction, Compound 10, (7.78 g) was added. The reaction mixture was heated to reflux for 2 hours. The reaction mixture was cooled to room temperature and 1N HCl was added to the reaction mixture until the pH became acidic. The crude product was extracted with EtOAc (50 mL×3) and the combined organic layers were washed with brine, were dried over Na2SO4 and concentrated. The residue, Compound 11, was heated with 10% H2SO4 (40 mL) at 100° C. overnight. The crude product was extracted with ethyl acetate (50 mL×3). The combined organic layers were dried over Na2SO4 and concentrated. The residue (2(S,R)-(methylethyl)-tetrahydrothiophen-3-one), compound 12, was dissolved in methylene chloride (60 mL) and the solution was cooled to 0° C. Diisobutylaluminumhydride (25 mL, 1M) in methylene chloride was added dropwise. The reaction mixture was stirred for one hour at 0° C. The reaction was quenched by the dropwise addition of water until no gas evolved. 1N HCl (50 mL) was added and the crude product was extracted with methylene chloride (50 mL×3). Combined organic layers were washed with saturated NaHCO3, brine and dried over Na2SO4. Concentration and purification by column chromatography, eluting with 20% ethyl acetate in hexane gave Compound 13, as an oil (1.72 g): to warm to room temperature was separated The aqueous layer was extracted with ethyl acetate (100 mL×3) The combined organic layers were dried over Na2SO4 concentrated Sodium (0.88 g) was dissolved in absolute ethanol (40 mL) at 0° C. the solution was concentrated The residue was dissolved in toluene the product from the previous reaction, Compound 10, (7.78 g) was added The reaction mixture was heated to reflux for 2 hours The reaction mixture was cooled to room temperature The crude product was extracted with EtOAc (50 mL×3) the combined organic layers were washed with brine were dried over Na2SO4 concentrated The residue, Compound 11, was heated with 10% H2SO4 (40 mL) at 100° C. overnight The crude product was extracted with ethyl acetate (50 mL×3) The combined organic layers were dried over Na2SO4 concentrated The residue (2(S,R)-(methylethyl)-tetrahydrothiophen-3-one), compound 12, was dissolved in methylene chloride (60 mL) the solution was cooled to 0° C Diisobutylaluminumhydride (25 mL, 1M) in methylene chloride was added dropwise The reaction mixture was stirred for one hour at 0° C The reaction was quenched by the dropwise addition of water until no gas 1N HCl (50 mL) was added the crude product was extracted with methylene chloride (50 mL×3) Combined organic layers were washed with saturated NaHCO3, brine dried over Na2SO4 Concentration and purification by column chromatography eluting with 20% ethyl acetate in hexane

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

Procedure: To a solution of NaH (60% dispersed in oil, 0.731 g, 21.7 mmol) in dry DMF (15 ml) was added Ethyl 3-mercaptopropionate (2.66 g, 19.8 mmol). When the evolution of hydrogen ceased, 4-Hydroxybenzyl bromide from Step A was added. The reaction mixture was stirred for 16 hours at room temperature, quenched with sat. NH4Cl and concentrated in vacuo. The crude residue was taken in EtOAc and washed with water and brine. The aqueous layer was washed one more time with EtOAc. The combined organic layers were dried over Na2SO4, filtered and concentrated. The purification was done by flash chromatography on silica gel column (dichloromethane:ethyl acetate, 95:5) to provide the title compound. quenched with sat. NH4Cl concentrated in vacuo washed with water and brine The aqueous layer was washed one more time with EtOAc The combined organic layers were dried over Na2SO4 filtered concentrated The purification

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

Procedure: To a solution of NaH (60% dispersed in oil, 0.731 g, 21.7 mmol) in dry DMF (15 ml) was added Ethyl 3-mercaptopropionate (2.66 g, 19.8 mmol). When the evolution of hydrogen ceased, 4-Hydroxybenzyl bromide from Step A was added. The reaction mixture was stirred for 16 hours at room temperature, quenched with sat. NH4Cl and concentrated in vacuo. The crude residue was taken in EtOAc and washed with water and brine. The aqueous layer was washed one more time with EtOAc. The combined organic layers were dried over Na2SO4, filtered and concentrated. The purification was done by flash chromatography on silica gel column (dichloromethane:ethyl acetate, 95:5) to provide the title compound. quenched with sat. NH4Cl concentrated in vacuo washed with water and brine The aqueous layer was washed one more time with EtOAc The combined organic layers were dried over Na2SO4 filtered concentrated The purification