4-(bromomethyl)-2-chlorobenzonitrile

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:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 17.3 g 2-Chloro-4-methyl-benzonitrile were dissolved in 50 ml tetrachloromethane and heated to reflux. A mixture of 24.3 g N-bromosuccinimide and 7.48 g 2,2′-azobis(2-methylpropionitrile) were added in five portions over a period of one hour. The reaction mixture was heated under reflux for additional three hours. The cooled reaction mixture was then filtered through a celite pad. The filtrate was washed with 100 ml saturated NaHCO3 solution, dried over MgSO4 and the solvent was removed in vacuo. The resulting residue was dissolved in 200 ml tetrahydrofuran and cooled in an ice bath to 0° C. 88.0 ml Diethyl phosphite were added, followed by the addition of 117.0 ml N,N-Diisopropylethylamine. The cooling bath was removed and the reaction mixture stirred at room temperature for four hours. The reaction mixture was poured in 400 ml 50% NaHCO3 solution and extracted with 400 ml diethylether. The organic layer was separated and washed with 200 ml 50% NaHCO3 solution and 200 ml water and then dried over MgSO4. The solvent was removed in vacuo. The resulting residue was purified on silica gel with the eluent n-heptane ethyl acetate=19:1 to obtain 13.0 g 4-Bromomethyl-2-chloro-benzonitrile as a solid. heated to reflux were added in five portions over a period of one hour The reaction mixture was heated under reflux for additional three hours The cooled reaction mixture was then filtered through a celite pad The filtrate was washed with 100 ml saturated NaHCO3 solution dried over MgSO4 the solvent was removed in vacuo The resulting residue was dissolved in 200 ml tetrahydrofuran 88.0 ml Diethyl phosphite were added followed by the addition of 117.0 ml N,N-Diisopropylethylamine The cooling bath was removed The reaction mixture was poured in 400 ml 50% NaHCO3 solution extracted with 400 ml diethylether The organic layer was separated washed with 200 ml 50% NaHCO3 solution and 200 ml water dried over MgSO4 The solvent was removed in vacuo The resulting residue was purified on silica gel with the eluent n-heptane ethyl acetate=19:1

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 17.3 g 2-Chloro-4-methyl-benzonitrile were dissolved in 50 ml tetrachloromethane and heated to reflux. A mixture of 24.3 g N-bromosuccinimide and 7.48 g 2,2′-azobis(2-methylpropionitrile) were added in five portions over a period of one hour. The reaction mixture was heated under reflux for additional three hours. The cooled reaction mixture was then filtered through a celite pad. The filtrate was washed with 100 ml saturated NaHCO3 solution, dried over MgSO4 and the solvent was removed in vacuo. The resulting residue was dissolved in 200 ml tetrahydrofuran and cooled in an ice bath to 0° C. 88.0 ml Diethyl phosphite were added, followed by the addition of 117.0 ml N,N-Diisopropylethylamine. The cooling bath was removed and the reaction mixture stirred at room temperature for four hours. The reaction mixture was poured in 400 ml 50% NaHCO3 solution and extracted with 400 ml diethylether. The organic layer was separated and washed with 200 ml 50% NaHCO3 solution and 200 ml water and then dried over MgSO4. The solvent was removed in vacuo. The resulting residue was purified on silica gel with the eluent n-heptane ethyl acetate=19:1 to obtain 13.0 g 4-Bromomethyl-2-chloro-benzonitrile as a solid. heated to reflux were added in five portions over a period of one hour The reaction mixture was heated under reflux for additional three hours The cooled reaction mixture was then filtered through a celite pad The filtrate was washed with 100 ml saturated NaHCO3 solution dried over MgSO4 the solvent was removed in vacuo The resulting residue was dissolved in 200 ml tetrahydrofuran 88.0 ml Diethyl phosphite were added followed by the addition of 117.0 ml N,N-Diisopropylethylamine The cooling bath was removed The reaction mixture was poured in 400 ml 50% NaHCO3 solution extracted with 400 ml diethylether The organic layer was separated washed with 200 ml 50% NaHCO3 solution and 200 ml water dried over MgSO4 The solvent was removed in vacuo The resulting residue was purified on silica gel with the eluent n-heptane ethyl acetate=19:1

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 2-amino-5-chloronicotinamide (0.14 g) in N,N-dimethylformamide (3 ml) was added 4-(bromomethyl)-2-chlorobenzonitrile (0.28 g), and the mixture was stirred at 100° C. for 14 hr. The reaction mixture was diluted with ethyl acetate. The precipitate was collected by filtration and washed with ethyl acetate. The obtained precipitate was recrystallized from methanol-ethyl acetate to give the title compound (85 mg). The precipitate was collected by filtration washed with ethyl acetate The obtained precipitate was recrystallized from methanol-ethyl acetate

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 17.3 g 2-Chloro-4-methyl-benzonitrile were dissolved in 50 ml tetrachloromethane and heated to reflux. A mixture of 24.3 g N-bromosuccinimide and 7.48 g 2,2′-azobis(2-methylpropionitrile) were added in five portions over a period of one hour. The reaction mixture was heated under reflux for additional three hours. The cooled reaction mixture was then filtered through a celite pad. The filtrate was washed with 100 ml saturated NaHCO3 solution, dried over MgSO4 and the solvent was removed in vacuo. The resulting residue was dissolved in 200 ml tetrahydrofuran and cooled in an ice bath to 0° C. 88.0 ml diethyl phosphite were added, followed by the addition of 117.0 ml N,N-diisopropylethylamine. The cooling bath was removed and the reaction mixture stirred at room temperature for four hours. The reaction mixture was poured in 400 ml 50% NaHCO3 solution and extracted with 400 ml diethylether. The organic layer was separated and washed with 200 ml 50% NaHCO3 solution and 200 ml water and then dried over MgSO4. The solvent was removed in vacuo. The resulting residue was purified on silica gel with the eluent n-heptane:ethyl acetate=19:1 to obtain 13.0 g 4-Bromomethyl-2-chloro-benzonitrile as a solid. heated to reflux were added in five portions over a period of one hour The reaction mixture was heated under reflux for additional three hours The cooled reaction mixture was then filtered through a celite pad The filtrate was washed with 100 ml saturated NaHCO3 solution dried over MgSO4 the solvent was removed in vacuo The resulting residue was dissolved in 200 ml tetrahydrofuran 88.0 ml diethyl phosphite were added followed by the addition of 117.0 ml N,N-diisopropylethylamine The cooling bath was removed The reaction mixture was poured in 400 ml 50% NaHCO3 solution extracted with 400 ml diethylether The organic layer was separated washed with 200 ml 50% NaHCO3 solution and 200 ml water dried over MgSO4 The solvent was removed in vacuo The resulting residue was purified on silica gel with the eluent n-heptane