hex-3-yn-2-one

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

Procedure: To a solution consisting of 6.06 parts of magnesium, 15 parts by volume of ether and 0.06 part of mercuric chloride, stirred at room temperature in an atmosphere of nitrogen, was added 0.5 part by volume of a solution consisting of 29.74 parts of propargyl bromide and 70 parts by volume of ether. The resulting mixture was then cooled to -10° to -15° and the remaining propargyl bromide solution was slowly added over a period of 45 minutes. At the end of the addition period, stirring was continued at -10° for about 15 minutes longer. To that mixture was then added, with stirring, over a period of 45 minutes at -3° to -5°, a mixture consisting of 22 parts of 3-hexyn-2-one and 60 parts by volume of benzene. At the end of the addition period, stirring was continued for about 20 minutes at -3°, and the reaction mixture was then poured carefully into cold dilute sulfuric acid. The aqueous phase was separated, extracted with ether and the combined ether extracts were washed with water, dried over anhydrous sodium sulfate and evaporated to dryness. Vacuum distillation of the residue afforded 4-methyl-1,5-octadiyn-4(RS)-ol, characterized by infrared absorption maxima of about 3620, 3330, 2250, 1385, 1355, 1085, 940, and 770 cm.-1. was added 0.5 part by volume of a solution The resulting mixture was then cooled to -10° to -15° At the end of the addition period stirring To that mixture was then added with stirring, over a period of 45 minutes at -3° to -5° At the end of the addition period stirring was continued for about 20 minutes at -3° The aqueous phase was separated extracted with ether the combined ether extracts were washed with water dried over anhydrous sodium sulfate evaporated to dryness Vacuum distillation of the residue

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

Procedure: To a solution consisting of 6.06 parts of magnesium, 15 parts by volume of ether and 0.06 part of mercuric chloride, stirred at room temperature in an atmosphere of nitrogen, was added 0.5 part by volume of a solution consisting of 29.74 parts of propargyl bromide and 70 parts by volume of ether. The resulting mixture was then cooled to -10° to -15° and the remaining propargyl bromide solution was slowly added over a period of 45 minutes. At the end of the addition period, stirring was continued at -10° for about 15 minutes longer. To that mixture was then added, with stirring, over a period of 45 minutes at -3° to -5°, a mixture consisting of 22 parts of 3-hexyn-2-one and 60 parts by volume of benzene. At the end of the addition period, stirring was continued for about 20 minutes at -3°, and the reaction mixture was then poured carefully into cold dilute sulfuric acid. The aqueous phase was separated, extracted with ether and the combined ether extracts were washed with water, dried over anhydrous sodium sulfate and evaporated to dryness. Vacuum distillation of the residue afforded 4-methyl-1,5-octadiyn-4(RS)-ol, characterized by infrared absorption maxima of about 3620, 3330, 2250, 1385, 1355, 1085, 940, and 770 cm.-1. was added 0.5 part by volume of a solution The resulting mixture was then cooled to -10° to -15° At the end of the addition period stirring To that mixture was then added with stirring, over a period of 45 minutes at -3° to -5° At the end of the addition period stirring was continued for about 20 minutes at -3° The aqueous phase was separated extracted with ether the combined ether extracts were washed with water dried over anhydrous sodium sulfate evaporated to dryness Vacuum distillation of the residue

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

Procedure: To a solution consisting of 6.06 parts of magnesium, 15 parts by volume of ether and 0.06 part of mercuric chloride, stirred at room temperature in an atmosphere of nitrogen, was added 0.5 part by volume of a solution consisting of 29.74 parts of propargyl bromide and 70 parts by volume of ether. The resulting mixture was then cooled to -10° to -15° and the remaining propargyl bromide solution was slowly added over a period of 45 minutes. At the end of the addition period, stirring was continued at -10° for about 15 minutes longer. To that mixture was then added, with stirring, over a period of 45 minutes at -3° to -5°, a mixture consisting of 22 parts of 3-hexyn-2-one and 60 parts by volume of benzene. At the end of the addition period, stirring was continued for about 20 minutes at -3°, and the reaction mixture was then poured carefully into cold dilute sulfuric acid. The aqueous phase was separated, extracted with ether and the combined ether extracts were washed with water, dried over anhydrous sodium sulfate and evaporated to dryness. Vacuum distillation of the residue afforded 4-methyl-1,5-octadiyn-4(RS)-ol, characterized by infrared absorption maxima of about 3620, 3330, 2250, 1385, 1355, 1085, 940, and 770 cm.-1. was added 0.5 part by volume of a solution The resulting mixture was then cooled to -10° to -15° At the end of the addition period stirring To that mixture was then added with stirring, over a period of 45 minutes at -3° to -5° At the end of the addition period stirring was continued for about 20 minutes at -3° The aqueous phase was separated extracted with ether the combined ether extracts were washed with water dried over anhydrous sodium sulfate evaporated to dryness Vacuum distillation of the residue

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

Procedure: A mixture of 5-amino-2,3-dihydrofuro[3,2-c]pyridin-5-ium 2,4-dinitrobenzenolate (2.00 g, 6.24 mmol), potassium carbonate (1.21 g, 8.75 mmol) and 3-hexyn-2-one (0.750 mL, 6.87 mmol) in dimethylformamide (30 mL) was stirred at 40° C. for 16 hr, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate and filtered. The solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (ethyl acetate/hexane=20/80→40/60) to give the title compound (314 mg, yield 22%). the mixture was extracted with ethyl acetate The extract was washed with saturated brine dried over anhydrous sodium sulfate filtered The solvent was evaporated under reduced pressure the residue was purified by silica gel column chromatography (ethyl acetate/hexane=20/80→40/60)

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

Procedure: A mixture of 5-amino-2,3-dihydrofuro[3,2-c]pyridin-5-ium 2,4-dinitrobenzenolate (2.00 g, 6.24 mmol), potassium carbonate (1.21 g, 8.75 mmol) and 3-hexyn-2-one (0.750 mL, 6.87 mmol) in dimethylformamide (30 mL) was stirred at 40° C. for 16 hr, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate and filtered. The solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (ethyl acetate/hexane=20/80→40/60) to give the title compound (314 mg, yield 22%). the mixture was extracted with ethyl acetate The extract was washed with saturated brine dried over anhydrous sodium sulfate filtered The solvent was evaporated under reduced pressure the residue was purified by silica gel column chromatography (ethyl acetate/hexane=20/80→40/60)

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

Procedure: A mixture of 5-amino-2,3-dihydrofuro[3,2-c]pyridin-5-ium 2,4-dinitrobenzenolate (2.00 g, 6.24 mmol), potassium carbonate (1.21 g, 8.75 mmol) and 3-hexyn-2-one (0.750 mL, 6.87 mmol) in dimethylformamide (30 mL) was stirred at 40° C. for 16 hr, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate and filtered. The solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (ethyl acetate/hexane=20/80→40/60) to give the title compound (314 mg, yield 22%). the mixture was extracted with ethyl acetate The extract was washed with saturated brine dried over anhydrous sodium sulfate filtered The solvent was evaporated under reduced pressure the residue was purified by silica gel column chromatography (ethyl acetate/hexane=20/80→40/60)

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of hex-3-yn-2-one (1.5 g, 15.6 mmol) in 90% ethanol (30 mL), cyanoacetamide (1.58 g, 18.72 mmol) and piperidine acetate {prepared by the addition of piperidine to a solution of acetic acid (0.258 mL) in water (0.65 mL) till pH 8} were added and reaction heated at 90° C. for 12 h. On completion, ethanol was evaporated and water was added to residue. Solid obtained was filtered and washed with water. Then this solid was stirred with acetonitrile for 10 min and filtered again to obtain the desired intermediate (1.5 g, 60%). were added reaction On completion, ethanol was evaporated water was added to residue Solid obtained was filtered washed with water filtered again

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of hex-3-yn-2-one (1.5 g, 15.6 mmol) in 90% ethanol (30 mL), cyanoacetamide (1.58 g, 18.72 mmol) and piperidine acetate {prepared by the addition of piperidine to a solution of acetic acid (0.258 mL) in water (0.65 mL) till pH 8} were added and reaction heated at 90° C. for 12 h. On completion, ethanol was evaporated and water was added to residue. Solid obtained was filtered and washed with water. Then this solid was stirred with acetonitrile for 10 min and filtered again to obtain the desired intermediate (1.5 g, 60%). were added reaction On completion, ethanol was evaporated water was added to residue Solid obtained was filtered washed with water filtered again

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of hex-3-yn-2-one (1.5 g, 15.6 mmol) in 90% ethanol (30 mL), cyanoacetamide (1.58 g, 18.72 mmol) and piperidine acetate {prepared by the addition of piperidine to a solution of acetic acid (0.258 mL) in water (0.65 mL) till pH 8} were added and reaction heated at 90° C. for 12 h. On completion, ethanol was evaporated and water was added to residue. Solid obtained was filtered and washed with water. Then this solid was stirred with acetonitrile for 10 min and filtered again to obtain the desired intermediate (1.5 g, 60%). were added reaction On completion, ethanol was evaporated water was added to residue Solid obtained was filtered washed with water filtered again