ethyl 2-bromo-2-cyanoacetate

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: A mixture of 1,1-dichloro-4-methylpenta-1,3-diene (30.2 parts), ethyl bromocyanoacetate (38.4 parts), calcium carbonate (20 parts), cuprous chloride (0.2 part) and calcium chloride (22.2 parts) in ethanol (100 parts by volume) is heated to reflux temperature and held at 78°-84° C. for 6 hours. The ethanol is distilled off under reduced pressure and the residue is stirred with a mixture of toluene (100 parts by volume), water (150 parts) and concentrated hydrochloric acid (100 parts by volume). The mixture is filtered from extraneous matter, the residue is washed with toluene and the filtrate and washings are combined. The toluene layer is separated and washed with water. The crude ethyl 1-cyano-3-(2',2'-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate is isolated by removal of the toluene under reduced pressure. The product has a strength of 74.6% and a cis-cyano/trans-cyano ratio of 86.1:13.9. The yield is 68.7%. is heated to reflux temperature The ethanol is distilled off under reduced pressure The mixture is filtered from extraneous matter the residue is washed with toluene The toluene layer is separated washed with water

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 1,1-dichloro-4-methylpenta-1,3-diene (30.2 parts), ethyl bromocyanoacetate (38.4 parts), calcium carbonate (20 parts), copper catalyst, phase transfer catalyst and calcium or sodium chloride (each as indicated in the table below) and water (100 parts) is heated at 80° C. and held at 80° C. for 6 hours. The reaction mixture is cooled and stirred with water (100 parts), butyl acetate (100 parts by volume) and concentrated hydrochloric acid (100 parts by volume). The mixture is filtered and the residue is washed with butyl acetate (2×20 parts by volume). The filtrate and washes are combined and the butyl acetate layer is separated and washed with water (4×50 parts). The crude ethyl-1-cyano-3-(2',2'-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate is isolated by removal of the butyl acetate under reduced pressure. The reaction mixture is cooled The mixture is filtered the residue is washed with butyl acetate (2×20 parts by volume) the butyl acetate layer is separated washed with water (4×50 parts)

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

実験手順: A mixture of 1,1-dichloro-4-methylpenta-1,3-diene (30.2 parts) and ethyl bromocyanoacetate (19.2 parts) is heated in ethanol (100 parts by volume) at 77°-80° C. for 6 hours in the presence of cupric chloride (1.34 parts) and calcium carbonate (10 parts). The crude ethyl 1-cyano-3-(2',2'-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate is isolated as described in Examples 13-24. The product has a strength of 61.0% and a cis-cyano/trans-cyano ratio of 85.2:14.8. The yield is 56.5%.

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

実験手順: A mixture of 1,1-dichloro-4-methylpenta-1,3-diene (15.1 parts) ethylbromocyanoacetate (19.2 parts), copper-containing catalyst (as indicated in the table below), acid binder (as indicated in the table below) in solvent (as indicated in the table below; 100 parts by volume) is heated to the reflux temperature of the mixture if below 90° C., otherwise at a temperature not exceeding 90° C., and held at the reaction temperature for 6 hours. After removal of the solvent by distillation under reduced pressure the residue is extracted with a mixture of toluene (100 parts by volume), water (150 parts) and concentrated hydrochloric acid (100 parts by volume). The extract is filtered, the toluene layer is separated, washed with water (4×50 parts) and the crude ethyl-1-cyano-3-(2',2'-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate is isolated by distilling off the toluene under reduced pressure. The yield, strength and composition of the product obtained is given in the table below together with other reaction details. containing catalyst ( 100 parts by volume) is heated to the reflux temperature of the mixture if below 90° C., otherwise at a temperature not exceeding 90° C. After removal of the solvent by distillation under reduced pressure the residue is extracted with a mixture of toluene (100 parts by volume), water (150 parts) and concentrated hydrochloric acid (100 parts by volume) The extract is filtered the toluene layer is separated washed with water (4×50 parts)

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

実験手順: A mixture of 1,1-dichloro-4-methylpenta-1,3-diene (15.1 parts) ethylbromocyanoacetate (19.2 parts), copper-containing catalyst (as indicated in the table below), acid binder (as indicated in the table below) in solvent (as indicated in the table below; 100 parts by volume) is heated to the reflux temperature of the mixture if below 90° C., otherwise at a temperature not exceeding 90° C., and held at the reaction temperature for 6 hours. After removal of the solvent by distillation under reduced pressure the residue is extracted with a mixture of toluene (100 parts by volume), water (150 parts) and concentrated hydrochloric acid (100 parts by volume). The extract is filtered, the toluene layer is separated, washed with water (4×50 parts) and the crude ethyl-1-cyano-3-(2',2'-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate is isolated by distilling off the toluene under reduced pressure. The yield, strength and composition of the product obtained is given in the table below together with other reaction details. containing catalyst ( 100 parts by volume) is heated to the reflux temperature of the mixture if below 90° C., otherwise at a temperature not exceeding 90° C. After removal of the solvent by distillation under reduced pressure the residue is extracted with a mixture of toluene (100 parts by volume), water (150 parts) and concentrated hydrochloric acid (100 parts by volume) The extract is filtered the toluene layer is separated washed with water (4×50 parts)

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

実験手順: A mixture of 1,1-dichloro-4-methylpenta-1,3-diene (15.1 parts), copper-containing catalyst in amount indicated in the table below and methanol (32 parts) is heated to reflux and ethyl bromocyanoacetate (19.2 parts) in methanol (14 parts) is then added at a uniform rate during 6 hours, and the acid-base balance ("pH" as indicated by a pH meter) is maintained at a predetermined value by the addition of a 13% solution of sodium methoxide in methanol. On completion of the ethyl bromocyanoacetate addition, heating at reflux temperature is continued for a further 2 hours, maintaining the desired acid-base balance as necessary. The resulting solution is evaporated under reduced pressure to remove the solvent and the product is isolated as described in Examples 2-6 above. The yield, strength and composition of the ethyl 1-cyano-3-(2',2'-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate obtained are given in the following table together with other reaction details: containing catalyst in amount is heated to reflux heating at reflux temperature maintaining the desired acid-base balance as necessary The resulting solution is evaporated under reduced pressure to remove the solvent the product is isolated

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: A mixture of 1,1-dichloro-4-methylpenta-1,3-diene (30.2 parts), ethyl bromocyanoacetate (38.4 parts), calcium carbonate (20 parts), cuprous chloride (0.2 part) and calcium chloride (22.2 parts) in ethanol (100 parts by volume) is heated to reflux temperature and held at 78°-84° C. for 6 hours. The ethanol is distilled off under reduced pressure and the residue is stirred with a mixture of toluene (100 parts by volume), water (150 parts) and concentrated hydrochloric acid (100 parts by volume). The mixture is filtered from extraneous matter, the residue is washed with toluene and the filtrate and washings are combined. The toluene layer is separated and washed with water. The crude ethyl 1-cyano-3-(2',2'-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate is isolated by removal of the toluene under reduced pressure. The product has a strength of 74.6% and a cis-cyano/trans-cyano ratio of 86.1:13.9. The yield is 68.7%. is heated to reflux temperature The ethanol is distilled off under reduced pressure The mixture is filtered from extraneous matter the residue is washed with toluene The toluene layer is separated washed with water

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 1,1-dichloro-4-methylpenta-1,3-diene (30.2 parts), ethyl bromocyanoacetate (38.4 parts), calcium carbonate (20 parts), copper catalyst, phase transfer catalyst and calcium or sodium chloride (each as indicated in the table below) and water (100 parts) is heated at 80° C. and held at 80° C. for 6 hours. The reaction mixture is cooled and stirred with water (100 parts), butyl acetate (100 parts by volume) and concentrated hydrochloric acid (100 parts by volume). The mixture is filtered and the residue is washed with butyl acetate (2×20 parts by volume). The filtrate and washes are combined and the butyl acetate layer is separated and washed with water (4×50 parts). The crude ethyl-1-cyano-3-(2',2'-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylate is isolated by removal of the butyl acetate under reduced pressure. The reaction mixture is cooled The mixture is filtered the residue is washed with butyl acetate (2×20 parts by volume) the butyl acetate layer is separated washed with water (4×50 parts)