prop-2-ene-1-thiol

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

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

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

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

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 1.14 ml of allyl mercaptan and 0.4 g of sodium hydroxide in 25 ml of water under an argon atmosphere was added a solution of 2.87 g of 4-acetoxy-3(S)-[1(R)-{dimethyl-{2-methylprop-2-yl}silyloxy}ethyl]azetidin-2-one in 10 ml of methanol. After 30 minutes, the mixture was partitioned between dichloromethane and water. The separated organic layer was washed with water, was dried over magnesium sulphate, evaporated to dryness, and then chromatographed on silica gel. Elution with ethyl acetate/hexane mixtures afforded 1.8 g of the title compound as white crystals. the mixture was partitioned between dichloromethane and water The separated organic layer was washed with water was dried over magnesium sulphate evaporated to dryness chromatographed on silica gel Elution with ethyl acetate/hexane

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

Procedure: To a solution of 1.06 g of sodium hydroxide in 14 ml of water were added 2.82 ml of allylthiol. The solution was stirred under an argon atmosphere for 10 minutes. To this solution was added, over a period of 1 minute, a solution of 3.79 g of ethyl acetoxyazetidinone in 6 ml of water. After about 15 minutes, when the starting material had been consumed, the solution was extracted three times with dichloromethane. The combined organic extracts were back-extracted with water, then dried over magnesium sulphate, evaporated in vacuo, and chromatographed over silica gel, eluting with ethyl acetate/hexane mixtures. The main product (2.84 g) was trans 4-allylthio-3-ethylazetidinone, which contained a trace amount of the cis isomer. (Yield 2.84 g) To this solution was added, over a period of 1 minute After about 15 minutes when the starting material had been consumed the solution was extracted three times with dichloromethane The combined organic extracts were back-extracted with water dried over magnesium sulphate evaporated in vacuo chromatographed over silica gel eluting with ethyl acetate/hexane mixtures

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

Procedure: A solution of 42.9 g of sodium hydroxide in 500 ml of water was made up under nitrogen and cooled to room temperature, 108 ml of allyl mercaptan were added and the mixture stirred under nitrogen for 30 minutes. 138.7 g of 4-acetoxyazetidin-2-one were added to the mixture over 10 minutes under nitrogen and the reaction mixture was stirred overnight. The reaction was checked for completion by T.L.C. (hexane-ethyl acetate) and extracted into dichloromethane (6×250 ml). The organic layer was washed with water (2×250 ml), dried over magnesium sulphate and evaporated in vacuo to dryness. Purification, over silica gel and elution with hexane-ethyl acetate afforded the above product as a yellow oil. (112.1 g, 73% of the theoretical yield). νmax=1769, 1778 (sh) cm-1. the reaction mixture was stirred overnight (hexane-ethyl acetate) and extracted into dichloromethane (6×250 ml) The organic layer was washed with water (2×250 ml) dried over magnesium sulphate evaporated in vacuo to dryness Purification over silica gel and elution with hexane-ethyl acetate

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

Procedure: Allyl mercaptan (2.12 g.) was added dropwise to a stirred suspension of ethyl 2-(2formamidothiazol-4-yl)-2-(2-bromoethoxyimino)acetate (syn isomer, 5 g.) and potassium carbonate (3.95 g.) in N,N-dimethylformamide (50 ml.) under ice cooling and stirred at the same temperature for 10 minutes and further at room temperature for 5 hours. After adding water (300 ml.) to the resultant solution, the mixture was extracted with ethyl acetate three times. The extracts were washed twice with a saturated aqueous solution of sodium chloride, dried over magnesium sulfate and concentrated in vacuo. The oily residue was subjected to column chromatography on silica gel and eluted with chloroform. The eluate was concentrated in vacuo to give ethyl 2-(2-allylthioethoxyimino)-2-(2-formamidothiazol-4-yl)acetate (syn isomer, 4.0 g.), mp. 62° to 64° C. the mixture was extracted with ethyl acetate three times The extracts were washed twice with a saturated aqueous solution of sodium chloride dried over magnesium sulfate concentrated in vacuo eluted with chloroform The eluate was concentrated in vacuo

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

Procedure: Allyl mercaptan (2.12 g.) was added dropwise to a stirred suspension of ethyl 2-(2formamidothiazol-4-yl)-2-(2-bromoethoxyimino)acetate (syn isomer, 5 g.) and potassium carbonate (3.95 g.) in N,N-dimethylformamide (50 ml.) under ice cooling and stirred at the same temperature for 10 minutes and further at room temperature for 5 hours. After adding water (300 ml.) to the resultant solution, the mixture was extracted with ethyl acetate three times. The extracts were washed twice with a saturated aqueous solution of sodium chloride, dried over magnesium sulfate and concentrated in vacuo. The oily residue was subjected to column chromatography on silica gel and eluted with chloroform. The eluate was concentrated in vacuo to give ethyl 2-(2-allylthioethoxyimino)-2-(2-formamidothiazol-4-yl)acetate (syn isomer, 4.0 g.), mp. 62° to 64° C. the mixture was extracted with ethyl acetate three times The extracts were washed twice with a saturated aqueous solution of sodium chloride dried over magnesium sulfate concentrated in vacuo eluted with chloroform The eluate was concentrated in vacuo

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

Procedure: 48 ml of allylmercaptan and 129.6 g of trityl alcohol were suspended in 500 ml of acetic acid and 2.0 ml of concentrated sulfuric acid was dropwise added thereto at room temperature with stirring. Then, the mixture was further stirred for one hour under the same conditions as above, and the precipitates were recovered therefrom by filtration, washed with 200 ml of methanol and then thoroughly washed with water. The resulting colorless powder was dissolved in benzene, washed with an aqueous 5% sodium hydrogen carbonate solution and then with water, and dried over anhydrous magnesium sulfate, and the solvent was removed therefrom by distillation under reduced pressure. The residue was treated with a small amount of methanol to obtain 130 g of allyl tritylsulfide (melting point: 99°-101° C.). Then, the mixture was further stirred for one hour under the same conditions as above, and the precipitates were recovered by filtration washed with 200 ml of methanol thoroughly washed with water The resulting colorless powder was dissolved in benzene washed with an aqueous 5% sodium hydrogen carbonate solution with water, and dried over anhydrous magnesium sulfate the solvent was removed by distillation under reduced pressure The residue was treated with a small amount of methanol