Diethyl 2-chloro-3-oxosuccinate

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

Procedure: A solution of diethyl 3-chloro-2-oxosuccinate (137.4 g, 0.69 mol), hexen-2-a1 (72.5 g, 0.74 mol) and ammonium sulphamate (190.2 g, 1.66 mol) in ethanol (450 ml) was stirred under reflux for 36 hours and then filtered. The filtrate was evaporated under vacuum, the resulting residue dissolved in water (500 ml) and this solution extracted with ethyl acetate (6×500 ml). The combined organic extracts were dried (MgSO4) and evaporated under vacuum, then the resulting residue was chromatographed on silica gel (50 g), using an ethyl acetate in hexane elution gradient (0-20% ethyl acetate), to give the title compound as an orange oil (34.1 g, 21%). Rf 0.20 (ethyl acetate:hexane, 20:80). under reflux for 36 hours filtered The filtrate was evaporated under vacuum the resulting residue dissolved in water (500 ml) this solution extracted with ethyl acetate (6×500 ml) The combined organic extracts were dried (MgSO4) evaporated under vacuum the resulting residue was chromatographed on silica gel (50 g) an ethyl acetate in hexane elution gradient (0-20% ethyl acetate)

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

Procedure: A stirred mixture of ethacrolein, (4.2 g, 0.05 mol), diethyl 3-chloro-2-oxo-butanedioate, (11.2 g, 0.05 mol) and ammonium sulfamate, (15.4 g, 0.135 mol) in ethanol (37 mL) is heated at reflux. After 15 hours the mixture is cooled to room temperature and the solvent removed by distillation under reduced pressure. The residue is treated with water and extracted with ethyl acetate. The organic phase is separated and concentrated in vacuo and the residue purified by column chromatography on silica gel using 4:1 hexane-ethyl acetate as the eluent to give 10.8 g (75% yield) of the title product as an oil which is shown to be 95% pure by a gas chromatography assay. is heated at reflux the solvent removed by distillation under reduced pressure The residue is treated with water extracted with ethyl acetate The organic phase is separated concentrated in vacuo the residue purified by column chromatography on silica gel using 4:1 hexane-ethyl acetate as the eluent

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

Procedure: A stirred mixture of ethacrolein, (4.2 g, 0.05 mol), diethyl 3-chloro-2-oxo-butanedioate, (11.2 g, 0.05 mol) and ammonium sulfamate, (15.4 g, 0.135 mol) in ethanol (37 mL) is heated at reflux. After 15 hours the mixture is cooled to room temperature and the solvent removed by distillation under reduced pressure. The residue is treated with water and extracted with ethyl acetate. The organic phase is separated and concentrated in vacuo and the residue purified by column chromatography on silica gel using 4:1 hexane-ethyl acetate as the eluent to give 10.8 g (75% yield) of the title product as an oil which is shown to be 95% pure by a gas chromatography assay. is heated at reflux the solvent removed by distillation under reduced pressure The residue is treated with water extracted with ethyl acetate The organic phase is separated concentrated in vacuo the residue purified by column chromatography on silica gel using 4:1 hexane-ethyl acetate as the eluent

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

Procedure: A solution of thiourea (1.7 g, 22 mmol) and diethyl 2-chloro-3-oxosuccinate (5.0 g, 22 mmol) in absolute ethanol (50 mL) was heated at reflux for one hour. After cooling to room temperature the solvent was removed leaving a white solid. The solid was dissolved in water (100 mL) and the resulting precipitate was filtered and dried (4.6 g, 87%). MS (ES): 245; at reflux for one hour was removed leaving a white solid the resulting precipitate was filtered dried (4.6 g, 87%)

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

Procedure: A solution of diethyl 3-chloro-2-oxosuccinate (137.4 g, 0.69 mol), hexen-2-al (72.5 g, 0.74 mol) and ammonium sulphamate (190.2 g, 1.66 mol) in ethanol (450 ml) was stirred under reflux for 36 hours and then filtered. The filtrate was evaporated under vacuum, the resulting residue dissolved in water (500 ml) and this solution extracted with ethyl acetate (6×500 ml). The combined organic extracts were dried (MgSO4) and evaporated under vacuum, then the resulting residue was chromatographed on silica gel (50 g), using an ethyl acetate in hexane elution gradient (0-20% ethyl acetate), to give the title compound as an orange oil (34.1 g, 21%). Rf 0.20 (ethyl acetate:hexane, 20:80). under reflux for 36 hours filtered The filtrate was evaporated under vacuum the resulting residue dissolved in water (500 ml) this solution extracted with ethyl acetate (6×500 ml) The combined organic extracts were dried (MgSO4) evaporated under vacuum the resulting residue was chromatographed on silica gel (50 g) an ethyl acetate in hexane elution gradient (0-20% ethyl acetate)

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

Procedure: A solution of diethyl 3-chloro-2-oxosuccinate (137.4 g, 0.69 mol), hexen-2-a1 (72.5 g, 0.74 mol) and ammonium sulphamate (190.2 g, 1.66 mol) in ethanol (450 ml) was stirred under reflux for 36 hours and then filtered. The filtrate was evaporated under vacuum, the resulting residue dissolved in water (500 ml) and this solution extracted with ethyl acetate (6×500 ml). The combined organic extracts were dried (MgSO4) and evaporated under vacuum, then the resulting residue was chromatographed on silica gel (50 g), using an ethyl acetate in hexane elution gradient (0-20% ethyl acetate), to give the title compound as an orange oil (34.1 g, 21%). Rf 0.20 (ethyl acetate:hexane, 20:80). under reflux for 36 hours filtered The filtrate was evaporated under vacuum the resulting residue dissolved in water (500 ml) this solution extracted with ethyl acetate (6×500 ml) The combined organic extracts were dried (MgSO4) evaporated under vacuum the resulting residue was chromatographed on silica gel (50 g) an ethyl acetate in hexane elution gradient (0-20% ethyl acetate)

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

Procedure: A stirred mixture of ethacrolein, (4.2 g, 0.05 mol), diethyl 3-chloro-2-oxo-butanedioate, (11.2 g, 0.05 mol) and ammonium sulfamate, (15.4 g, 0.135 mol) in ethanol (37 mL) is heated at reflux. After 15 hours the mixture is cooled to room temperature and the solvent removed by distillation under reduced pressure. The residue is treated with water and extracted with ethyl acetate. The organic phase is separated and concentrated in vacuo and the residue purified by column chromatography on silica gel using 4:1 hexane-ethyl acetate as the eluent to give 10.8 g (75% yield) of the title product as an oil which is shown to be 95% pure by a gas chromatography assay. is heated at reflux the solvent removed by distillation under reduced pressure The residue is treated with water extracted with ethyl acetate The organic phase is separated concentrated in vacuo the residue purified by column chromatography on silica gel using 4:1 hexane-ethyl acetate as the eluent