1-(2-chlorophenyl)-3-(dimethylamino)prop-2-en-1-one

反応条件: temp:83.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a 5 liter, 3-necked flask equipped with a mechanical stirrer, thermometer, reflux condenser capped with a nitrogen inlet, and a heating mantle were added o-chloroacetophenone (305.8 g), N,N-dimethylformamide dimethyl acetal (707.0 g), and acetonitrile (dried over molecular sieves, 3.0 L) giving an orange solution. The mixture was heated gradually to reflux (83° C.) over 1.5 hours, then maintained at reflux for 18 hours. After the dark red solution was cooled to room temperature, the acetonitrile was evaporated, leaving a heavy red oil. The oil was redissolved in toluene (1L). The toluene was evaporated to afford the crude enamine which was further dried under high vacuum overnight to afford 2'-chloro-3-dimethylaminopropenophenone (422 g) which was used without further purification. To a 5 liter, 3-necked flask equipped with a mechanical stirrer thermometer, reflux condenser capped with a nitrogen inlet giving an orange solution The mixture was heated gradually maintained at reflux for 18 hours After the dark red solution was cooled to room temperature the acetonitrile was evaporated leaving a heavy red oil The toluene was evaporated to afford the crude enamine which was further dried under high vacuum overnight

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 7 g (0.0540 mol) of hydrazine hydrate are added, slowly and at room temperature, to a solution of 10.5 g (0.050 mol) of 1-(2-chlorophenyl)-3-dimethylamino-2-propen-1-one, prepared in Example 1, in 60 ml of ethanol. The reaction mixture is stirred for 5 hours at room temperature then left standing for 12 hours before being concentrated to dryness. The residue is recrystallised from a heptane/ethyl acetate mixture. 6.9 g (0.0386 mol) of 3-(2'-chlorophenyl)-1H-pyrazole are obtained, which melts at 93° C. (yield 77%) (compound 60). then left standing for 12 hours before being concentrated to dryness The residue is recrystallised from a heptane/ethyl acetate mixture

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 7 g (0.0540 mol) of hydrazine hydrate are added, slowly and at room temperature, to a solution of 10.5 g (0.050 mol) of 1-(2-chlorophenyl)-3-dimethylamino-2-propen-1-one, prepared in Example 1, in 60 ml of ethanol. The reaction mixture is stirred for 5 hours at room temperature then left standing for 12 hours before being concentrated to dryness. The residue is recrystallised from a heptane/ethyl acetate mixture. 6.9 g (0.0386 mol) of 3-(2'-chlorophenyl)-1H-pyrazole are obtained, which melts at 93° C. (yield 77%) (compound 60). then left standing for 12 hours before being concentrated to dryness The residue is recrystallised from a heptane/ethyl acetate mixture

反応条件: temp:83.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a 5 liter, 3-necked flask equipped with a mechanical stirrer, thermometer, reflux condenser capped with a nitrogen inlet, and a heating mantle were added o-chloroacetophenone (305.8 g), N,N-dimethylformamide dimethyl acetal (707.0 g), and acetonitrile (dried over molecular sieves, 3.0 L) giving an orange solution. The mixture was heated gradually to reflux (83° C.) over 1.5 hours, then maintained at reflux for 18 hours. After the dark red solution was cooled to room temperature, the acetonitrile was evaporated, leaving a heavy red oil. The oil was redissolved in toluene (1 L). The toluene was evaporated to afford the crude enamine which was further dried under high vacuum overnight to afford 2'-chloro-3-dimethylaminopropenophenone (422 g) which was used without further purification. To a 5 liter, 3-necked flask equipped with a mechanical stirrer thermometer, reflux condenser capped with a nitrogen inlet giving an orange solution The mixture was heated gradually maintained at reflux for 18 hours After the dark red solution was cooled to room temperature the acetonitrile was evaporated leaving a heavy red oil The toluene was evaporated to afford the crude enamine which was further dried under high vacuum overnight

反応条件: temp:83.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a 5 liter, 3-necked flask equipped with a mechanical stirrer, thermometer, reflux condenser capped with a nitrogen inlet, and a heating mantle were added o-chloroacetophenone (305.8 g, 1.98 mol), N,N-dimethylformamide dimethyl acetal (707.0 g, 5.93 mol), and acetonitrile (dried over molecular sieves, 3.0 L) at room temperature, giving an orange solution. The mixture was heated gradually to reflux (83° C.) over 1.5 hours, then maintained at reflux for 18 hours. After the dark red solution was cooled to room temperature, the acetonitrile was evaporated, leaving a heavy red oil. The oil was redissolved in toluene (1 L). The toluene was evaporated to afford the crude enamine which was further dried under high vacuum overnight to afford 2'-chloro-3-dimethylaminopropenophenone (422 g, quantitative) which was used without further purification. To a 5 liter, 3-necked flask equipped with a mechanical stirrer thermometer, reflux condenser capped with a nitrogen inlet giving an orange solution The mixture was heated gradually maintained at reflux for 18 hours After the dark red solution was cooled to room temperature the acetonitrile was evaporated leaving a heavy red oil The toluene was evaporated to afford the crude enamine which was further dried under high vacuum overnight

反応条件: temp:83.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a 5 liter, 3-necked flask equipped with a mechanical stirrer, thermometer, reflux condenser capped with a nitrogen inlet, and a heating mantle were added o-chloroacetophenone (305.8 g), N,N-dimethylformamide dimethyl acetal (707.0 g), and acetonitrile (dried over molecular sieves, 3.0 L) giving an orange solution. The mixture was heated gradually to reflux (83° C.) over 1.5 hours, then maintained at reflux for 18 hours. After the dark red solution was cooled to room temperature, the acetonitrile was evaporated, leaving a heavy red oil. The oil was redissolved in toluene (1L). The toluene was evaporated to afford the crude enamine which was further dried under high vacuum overnight to afford 2'-chloro-3-dimethylaminopropenophenone (422 g) which was used without further purification. To a 5 liter, 3-necked flask equipped with a mechanical stirrer thermometer, reflux condenser capped with a nitrogen inlet giving an orange solution The mixture was heated gradually maintained at reflux for 18 hours After the dark red solution was cooled to room temperature the acetonitrile was evaporated leaving a heavy red oil The toluene was evaporated to afford the crude enamine which was further dried under high vacuum overnight

反応条件: temp:83.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a 5 liter, 3-necked flask equipped with a mechanical stirrer, thermometer, reflux condenser capped with a nitrogen inlet, and a heating mantle were added o-chloroacetophenone (305.8 g), N,N-dimethylformamide dimethyl acetal (707.0 g), and acetonitrile (dried over molecular sieves, 3.0 L) giving an orange solution. The mixture was heated gradually to reflux (83° C.) over 1.5 hours, then maintained at reflux for 18 hours. After the dark red solution was cooled to room temperature, the acetonitrile was evaporated, leaving a heavy red oil. The oil was redissolved in toluene (1L). The toluene was evaporated to afford the crude enamine which was further dried under high vacuum overnight to afford 2'-chloro-3-dimethylaminopropenophenone (422 g) which was used without further purification. To a 5 liter, 3-necked flask equipped with a mechanical stirrer thermometer, reflux condenser capped with a nitrogen inlet giving an orange solution The mixture was heated gradually maintained at reflux for 18 hours After the dark red solution was cooled to room temperature the acetonitrile was evaporated leaving a heavy red oil The toluene was evaporated to afford the crude enamine which was further dried under high vacuum overnight

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 7 g (0.0540 mol) of hydrazine hydrate are added, slowly and at room temperature, to a solution of 10.5 g (0.050 mol) of 1-(2-chlorophenyl)-3-dimethylamino-2-propen-1-one, prepared in Example 1, in 60 ml of ethanol. The reaction mixture is stirred for 5 hours at room temperature then left standing for 12 hours before being concentrated to dryness. The residue is recrystallised from a heptane/ethyl acetate mixture. 6.9 g (0.0386 mol) of 3-(2'-chlorophenyl)-1H-pyrazole are obtained, which melts at 93° C. (yield 77%) (compound 60). then left standing for 12 hours before being concentrated to dryness The residue is recrystallised from a heptane/ethyl acetate mixture

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 25 g. of o-chloroacetophenone and 25 ml. of dimethylformamide dimethylacetal is refluxed for 16 hours. Evaporation gives a thick red-brown oil which is dissolved in methylene chloride and this solution passed through a hydrous magnesium silicate column. Evaporation of solvent gives an oil which is then purified by bulb to bulb distillation. A mixture of 25 g Evaporation gives a thick red-brown oil which Evaporation of solvent gives an oil which is then purified by bulb to bulb distillation

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 7 g (0.0540 mol) of hydrazine hydrate are added, slowly and at room temperature, to a solution of 10.5 g (0.050 mol) of 1-(2-chlorophenyl)-3-dimethylamino-2-propen-1-one, prepared in Example 1, in 60 ml of ethanol. The reaction mixture is stirred for 5 hours at room temperature then left standing for 12 hours before being concentrated to dryness. The residue is recrystallised from a heptane/ethyl acetate mixture. 6.9 g (0.0386 mol) of 3-(2'-chlorophenyl)-1H-pyrazole are obtained, which melts at 93° C. (yield 77%) (compound 60). then left standing for 12 hours before being concentrated to dryness The residue is recrystallised from a heptane/ethyl acetate mixture

反応条件: temp:83.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a 5 liter, 3-necked flask equipped with a mechanical stirrer, thermometer, reflux condenser capped with a nitrogen inlet, and a heating mantle were added o-chloroacetophenone (305.8 g), N,N-dimethylformamide dimethyl acetal (707.0 g), and acetonitrile (dried over molecular sieves, 3.0 L) giving an orange solution. The mixture was heated gradually to reflux (83° C.) over 1.5 hours, then maintained at reflux for 18 hours. After the dark red solution was cooled to room temperature, the acetonitrile was evaporated, leaving a heavy red oil. The oil was redissolved in toluene (1 L). The toluene was evaporated to afford the crude enamine which was further dried under high vacuum overnight to afford 2'-chloro-3-dimethylaminopropenophenone (422 g) which was used without further purification. To a 5 liter, 3-necked flask equipped with a mechanical stirrer thermometer, reflux condenser capped with a nitrogen inlet giving an orange solution The mixture was heated gradually maintained at reflux for 18 hours After the dark red solution was cooled to room temperature the acetonitrile was evaporated leaving a heavy red oil The toluene was evaporated to afford the crude enamine which was further dried under high vacuum overnight

反応条件: temp:83.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a 5 liter, 3-necked flask equipped with a mechanical stirrer, thermometer, reflux condenser capped with a nitrogen inlet, and a heating mantle were added o-chloroacetophenone (305.8 g, 1.98 mol), N,N-dimethylformamide dimethyl acetal (707.0 g, 5.93 mol), and acetonitrile (dried over molecular sieves, 3.0 L) at room temperature, giving an orange solution. The mixture was heated gradually to reflux (83° C.) over 1.5 hours, then maintained at reflux for 18 hours. After the dark red solution was cooled to room temperature, the acetonitrile was evaporated, leaving a heavy red oil. The oil was redissolved in toluene (1 L). The toluene was evaporated to afford the crude enamine which was further dried under high vacuum overnight to afford 2'-chloro-3-dimethylaminopropenophenone (422 g, quantitative) which was used without further purification. To a 5 liter, 3-necked flask equipped with a mechanical stirrer thermometer, reflux condenser capped with a nitrogen inlet giving an orange solution The mixture was heated gradually maintained at reflux for 18 hours After the dark red solution was cooled to room temperature the acetonitrile was evaporated leaving a heavy red oil The toluene was evaporated to afford the crude enamine which was further dried under high vacuum overnight