4-甲基戊烷-1,2-二醇

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 296.9 g of 1,2-dichloroethane (3 mol), 15 g of polyethylene glycol dimethyl ether (mean molar mass 500 g/mol) and 177.1 g of potassium carbonate (1.265 mol) were initially introduced, and the reaction mixture was heated until the 1,2-dichloroethane refluxes. 125.5 g of dimethyl malonate (0.95 mol) and 1.25 g of tetrabutylammonium bromide (3.88 mmol) were then added at the boil. The mixture was stirred using a paddle stirrer for 6 hours. Water formed during the reaction was removed by azeotropic distillation with 1,2-dichloroethane throughout the reaction. Further work-up was carried out analogously to Comparative Example 2. The yield was 95%. for 6 hours was removed by azeotropic distillation with 1,2-dichloroethane throughout the reaction

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 450.3 g of 1,2-dichloroethane (4.55 mol), 15.5 g of polyethylene glycol dimethyl ether (mean molar mass 250 g/mol) and 168.0 g of potassium carbonate (1.2 mol) were initially introduced, and the reaction mixture was heated until the 1,2-dichloroethane refluxes. 118.9 g of dimethyl malonate (0.9 mol) and 1.25 g of tetrabutylammonium bromide (3.88 mmol) were then added at the boil. The mixture was stirred using a finely dispersing stirrer (Ultra Turrax) for 6 hours. Water formed during the reaction was removed by azeotropic distillation with 1,2-dichloroethane throughout the reaction. Further work-up was carried out analogously to Comparative Example 2. The yield was 96.3%. a finely dispersing stirrer (Ultra Turrax) for 6 hours was removed by azeotropic distillation with 1,2-dichloroethane throughout the reaction

反应条件: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 100 ml flange flask fitted with a distillation bridge and anchor stirrer, 14.5 g (0.25 mol) of potassium fluoride, 4.8 g (0.007 mol) of trimethyl(ethoxypolyoxypropyl)ammonium chloride, 6.2 g (0.012 mol) of polyethylene glycol dimethyl ether 500 and 2.4 g (0.007 mol) of tetrabutylphosphonium bromide were introduced at 100° C. into the melt of 47.5 g (0.25 mol) of 2,4-dichloro-5-fluorobenzonitrile. Subsequently, 10 g (0.09 mol) of xylene were added and the reaction suspension was azeotropically dried by application of a vacuum of 20 mbar and heating to 130° C. After the xylene had been distilled off, the reaction suspension was heated to 140° C. and stirred for 8 hours at this temperature. Amount of 2-chloro-4,5-difluorobenzonitrile formed: the reaction suspension was azeotropically dried by application of a vacuum of 20 mbar After the xylene had been distilled off the reaction suspension was heated to 140° C.

反应条件: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 100 ml flange flask fitted with a distillation bridge and anchor stirrer, 14.5 g (0.25 mol) of potassium fluoride, 4.8 g (0.007 mol) of trimethyl(ethoxypolyoxypropyl)ammonium chloride, 6.2 g (0.012 mol) of polyethylene glycol dimethyl ether 500 and 2.4 g (0.007 mol) of tetrabutylphosphonium bromide were introduced at 100° C. into the melt of 47.5 g (0.25 mol) of 2,4-dichloro-5-fluorobenzonitrile. Subsequently, 10 g (0.09 mol) of xylene were added and the reaction suspension was azeotropically dried by application of a vacuum of 20 mbar and heating to 130° C. After the xylene had been distilled off, the reaction suspension was heated to 140° C. and stirred for 8 hours at this temperature. Amount of 2-chloro-4,5-difluorobenzonitrile formed: the reaction suspension was azeotropically dried by application of a vacuum of 20 mbar After the xylene had been distilled off the reaction suspension was heated to 140° C.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 250 ml flange flask and fitted with an impeller stirrer, 69.6 g (1.2 mol) of potassium fluoride, 6.9 g (0.02 mol) of tetrabutyl-phosphonium bromide, 13.8 g (0.02 mol) of dimethyldi(ethoxypolyoxypropyl)ammonium chloride, 13.8 g (0.028 mol) of polyethylene glycol dimethyl ether 500 and 20 g of xylene were metered at 120° C. into the melt of 137.6 g (1.0 mol) of 4-chlorobenzonitrile. After stirring for 30 minutes, the reaction suspension was azeotropically dried by distilling off the xylene under vacuum. The reaction suspension was stirred for 30 hours at 190° C. Amount of 4-fluorobenzonitrile formed: after 9 hours: 12 GC area-% after 30 hours: 48 GC area-%, besides 45 GC area-% of unreacted 4-chlorobenzonitrile. In a 250 ml flange flask and fitted with an impeller stirrer the reaction suspension was azeotropically dried by distilling off the xylene under vacuum The reaction suspension was stirred for 30 hours at 190° C

反应条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 1.5 liter flange flask and fitted with a distillation bridge and impeller stirrer, 279 g (4.8 tool) of fluoride, 218.5 g (0.3 mol) of trimethyl(ethoxypolyoxypropyl)ammonium chloride and 11.5 g (0.023 mol) of polyethylene glycol dimethyl ether 500 were introduced at 100° C. into the melt of 768 g (4 mol) of 2,3-dichloronitrobenzene. Subsequently, the mixture was azeotropically dried using 200 g (1.9 mol) of xylene and stirred for 24 hours at a temperature of 100° C. Amount of 3-chloro-2-fluoronitrobenzene formed: after 5 hours: 18 GC area-%. after 24 hours: 47 GC area-%. Subsequently, the mixture was azeotropically dried

反应条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 1.5 liter flange flask and fitted with a distillation bridge and impeller stirrer, 279 g (4.8 tool) of fluoride, 218.5 g (0.3 mol) of trimethyl(ethoxypolyoxypropyl)ammonium chloride and 11.5 g (0.023 mol) of polyethylene glycol dimethyl ether 500 were introduced at 100° C. into the melt of 768 g (4 mol) of 2,3-dichloronitrobenzene. Subsequently, the mixture was azeotropically dried using 200 g (1.9 mol) of xylene and stirred for 24 hours at a temperature of 100° C. Amount of 3-chloro-2-fluoronitrobenzene formed: after 5 hours: 18 GC area-%. after 24 hours: 47 GC area-%. Subsequently, the mixture was azeotropically dried

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 97.6 g (0.4 mol) of 5-bromo-2,4-dichlorofluorobenzene, 35.8 g (0.4 mol) of copper(I)cyanide, 10.0 g (0.014 mol) of trimethyl(ethoxypolyoxypropyl)ammonium chloride, 5.0 g (0.015 mol) of tetrabutylphosphonium bromide and 5.0 g (0.01 mol) of polyethylene glycol dimethyl ether 500 were introduced together with 20.0 g (0.19 mol) of xylene into a 250 ml 3-neck flask fitted with a reflux condenser and blade stirrer and azeotropically dried at up to 150° C. under reduced pressure. Amount of 2,4-dichloro-5-fluorobenzonitrile formed: after 5 hours: 19 GC area-%. after 26 hours: 75 GC area-%. fitted with a reflux condenser and blade stirrer azeotropically dried at up to 150° C. under reduced pressure

反应条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 2 liter flange flask and fitted with a distillation bridge and impeller stirrer, 290.5 g (5.0 mol) of potassium fluoride, 71.1 g (0.1 mol) of trimethyl(ethoxypolyoxypropyl)ammonium chloride, 11.0 g (0.1 mol) of tetramethylammonium chloride and 17.7 g (0.035 mol) of polyethylene glycol dimethyl ether 500 were introduced at 120° C. into the melt of 630 g (4.0 mol) of 2-chloronitrobenzene. Subsequently, the mixture was azeotropically dried using 100 g (0.94 mol) of xylene and the reaction mixture was stirred for 28 hours at a temperature of 150° C. Amount of 2-fluoronitrobenzene formed: after 6 hours: 36 GC area-%. after 28 hours: 74 GC area-%. Subsequently, the mixture was azeotropically dried

反应条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 2 liter flange flask and fitted with a distillation bridge and impeller stirrer, 290.5 g (5.0 mol) of potassium fluoride, 71.1 g (0.1 mol) of trimethyl(ethoxypolyoxypropyl)ammonium chloride, 11.0 g (0.1 mol) of tetramethylammonium chloride and 17.7 g (0.035 mol) of polyethylene glycol dimethyl ether 500 were introduced at 120° C. into the melt of 630 g (4.0 mol) of 2-chloronitrobenzene. Subsequently, the mixture was azeotropically dried using 100 g (0.94 mol) of xylene and the reaction mixture was stirred for 28 hours at a temperature of 150° C. Amount of 2-fluoronitrobenzene formed: after 6 hours: 36 GC area-%. after 28 hours: 74 GC area-%. Subsequently, the mixture was azeotropically dried

反应条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 2-liter flange flask fitted with a distillation bridge and impeller stirrer, 290.5 g (5.0 mol) of potassium fluoride, 71.1 g (0.1 mol) of trimethyl (ethoxypolyoxypropyl) ammonium chloride, 11.0 g (0.1 mol) of tetramethylammonium chloride and 17.7 g (0.035 mol) of polyethylene glycol dimethyl ether 500 were introduced at 120° C. into the melt of 630 g (4.0 mol) of 2-chloronitrobenzene. Subsequently, 100 g (0.38 mol) of xylene were added and the reaction mixture was stirred for 21 hours at a temperature of 150° C. Amount of 2-fluoronitrobenzene formed, according to GC analysis:

反应条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 1-liter flange flask fitted with a distillation bridge and stirrer, 29 g (0.06 mol) of polyethylene glycol dimethyl ether 500 and 139 g (2.4 mol) of potassium fluoride were introduced at 120° C. into the melt of 576 g (3.0 mol) of 2,3-dichloronitrobenzene. Subsequently, 20 g (0.19 mol) of xylene were added and the reaction suspension was azeotropically dried by application of a vacuum of 60 mbar and heating to 150° C. After the xylene had been distilled off, the distillation bridge was replaced by a reflux condenser, the reaction suspension was heated to 190° C. and stirred for 6 hours at this temperature. Amount of 3-chloro-2-fluoronitrobenzene formed: 11 GC area-% after 6 hours. the reaction suspension was azeotropically dried by application of a vacuum of 60 mbar After the xylene had been distilled off the distillation bridge was replaced by a reflux condenser the reaction suspension was heated to 190° C.