(2-amino-2-sulfanylideneethyl) acetate

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

Procedure: 2-Bromoacetophenone (39.9 g; 0.2 mole) and 2-acetoxythioacetamide (30 g; 0.225 mole) were dissolved in dioxan (150 ml). The mixture was stirred and heated on a steam bath for 15 minutes, yielding a mass of crystals. Aqueous 5N HCl (40 ml) was added and the heating continued for a further 30 minutes. The dioxan was evaporated under vacuum and the residue neutralised with aqueous Na2CO3 solution. The solid was collected, washed with water and dried. After recrystallisation from benzene the product weighed 33.5 g (87%) and had a m.p. of 88°-9° C. heated on a steam bath for 15 minutes yielding a mass of crystals The dioxan was evaporated under vacuum The solid was collected washed with water dried After recrystallisation from benzene the product

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

Procedure: A mixture of 5.33 g of 2-acetoxythioacetamide prepared according to Example 2, 5.21 g of 1,3-dichloroacetone, 6.88 g of sodium bicarbonate and 20 ml of 1,2-dichloroethane was stirred at room temperature for 87 hours. The mixture was filtered to remove insoluble inorganics and concentrated under reduced pressure to an oil. The oil was taken up in 4 mls of 1,2-dichloroethane and 25 mils of cyclohexane added dropwise. The slurry was stirred for 1 hour at 0° C. and then filtered. The precipitate was washed with cyclohexane and dried at room temperature under reduced pressure. The product 2-acetoxymethyl-4-chloromethyl-4-hydroxy-thiazoline was obtained in 92% yield (8.25 g). prepared The mixture was filtered to remove insoluble inorganics concentrated under reduced pressure to an oil 25 mils of cyclohexane added dropwise The slurry was stirred for 1 hour at 0° C. filtered The precipitate was washed with cyclohexane dried at room temperature under reduced pressure

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 5.33 g of 2-acetoxythioacetamide, prepared according to Example 2, 5.21 g of 1,3-dichloroacetone, 3.44 g of sodium bicarbonate and 20 ml of 1,2-dichloroethane was heated at 40° C. for 15 hours. The mixture was filtered to remove insoluble inorganics and concentrated under reduced pressure to an oil. The oil was taken up in 25 ml of isopropyl alcohol saturated with hydrogen chloride (5N) and 25 ml of isopropanol added to improve stirring. The slurry was stirred for 30 minutes at 0° C. and then filtered. The precipitate was washed with cold IPA and dried at room temperature under reduced pressure. The product 2-acetoxymethyl-4-chloromethyl-4-hydroxythiazoline hydrochloride was obtained in 60% yield (1.66 g). prepared The mixture was filtered to remove insoluble inorganics concentrated under reduced pressure to an oil added The slurry was stirred for 30 minutes at 0° C. filtered The precipitate was washed with cold IPA dried at room temperature under reduced pressure

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

Procedure: A mixture of 5.33 g of 2-acetoxythioacetamide prepared according to Example 2, 5.21 g of 1,3-dichloroacetone, 6.88 g of sodium bicarbonate and 20 ml of 1,2-dichloroethane was stirred at room temperature for 87 hours. The mixture was filtered to remove insoluble inorganics and concentrated under reduced pressure to an oil. The oil was taken up in 4 mls of 1,2-dichloroethane and 25 mls of cyclohexane added dropwise. The slurry was stirred for 1 hour at 0° C. and then filtered. The precipitate was washed with cyclohexane and dried at room temperature under reduced pressure. The product, 2-acetoxymethyl-4-chloromethyl-4-hydroxy-thiazoline was obtained in 92% yield (8.25 g). prepared The mixture was filtered to remove insoluble inorganics concentrated under reduced pressure to an oil 25 mls of cyclohexane added dropwise The slurry was stirred for 1 hour at 0° C. filtered The precipitate was washed with cyclohexane dried at room temperature under reduced pressure

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 5.33 g of 2-acetoxythioacetamide, prepared according to Example 2, 5.21 g of 1,3-dichloroacetone, 3.44 g of sodium bicarbonate and 20 ml of 1,2-dichloroethane was heated at 40° C. for 15 hours. The mixture was filtered to remove insoluble inorganics and concentrated under reduced pressure to an oil. The oil was taken up in 25 ml of isopropyl alcohol saturated with hydrogen chloride (5N) and 25 ml of isopropanol added to improve stirring. The slurry was stirred for 30 minutes at 0° C. and then filtered. The precipitate was washed with cold IPA and dried at room temperature under reduced pressure. The product 2-acetoxymethyl-4-chloromethyl-4-hydroxythiazoline hydrochloride was obtained in 60% yield (1.66 g). prepared The mixture was filtered to remove insoluble inorganics concentrated under reduced pressure to an oil added The slurry was stirred for 30 minutes at 0° C. filtered The precipitate was washed with cold IPA dried at room temperature under reduced pressure

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2-acetoxythioacetamide (10 g), 2-chlorocyclopentanone (10.6 g) and dimethylformamide (100 ml) was stirred for 24 hours at 80° C. The reaction mixture was cooled and poured into ice-water (500 ml), followed by extraction twice with ethyl acetate (200 ml). The extract was washed twice with water (100 ml), which was dried over magnesium sulfate, then the solvent was distilled off under reduced pressure. The residue was subjected to a silica gel chromatography (2.5×50 cm), eluting with ethyl acetate-hexane (3:7). The object fraction was concentrated to give 2-acetoxymethyl-5,6-dihydro-4H-cyclopentathiazole (5 g) as a yellow oily product. The reaction mixture was cooled followed by extraction twice with ethyl acetate (200 ml) The extract was washed twice with water (100 ml), which was dried over magnesium sulfate the solvent was distilled off under reduced pressure eluting with ethyl acetate-hexane (3:7) The object fraction was concentrated