methyl 3-(bromomethyl)-2-chlorobenzoate

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:

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: To a solution of methyl 3-(bromomethyl)-2-chlorobenzoate (748 mg, 2.84 mmol) in N,N-dimethylformamide (7 mL) was added sodium cyanide (412 mg, 8.41 mmol), and the mixture was stirred under a nitrogen stream at 80° C. for 1 hr. The reaction mixture was diluted with a mixed solvent of ethyl acetate and hexane (1:1). The solution was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered. The solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate=98/2→80/20) and crystallized from ethyl acetate/hexane to give the title compound (470 mg, 79%) as white crystals. The solution was washed with water and saturated brine dried over anhydrous magnesium sulfate filtered The solvent was evaporated under reduced pressure the obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate=98/2→80/20) crystallized from ethyl acetate/hexane

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of methyl 2-chloro-3-methylbenzoate (3.60 g, 19.4 mmol) in acetonitrile (60 mL) were added 1-bromopyrrolidine-2,5-dione (11.46 g, 64.3 mmol) and 2,2′-(E)-diazene-1,2-diylbis(2-methylpropanenitrile) (960 mg, 5.84 mmol), and the mixture was stirred at 90° C. for 26 hr. The reaction mixture was concentrated, insoluble material was filtered off, and the filtrate was concentrated. The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate=100/0→95/5) to give the title compound (3.42 g, 66%) as a colorless oil. The reaction mixture was concentrated insoluble material was filtered off the filtrate was concentrated The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate=100/0→95/5)

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

実験手順: To a solution of methyl 3-(bromomethyl)-2-chlorobenzoate (748 mg, 2.84 mmol) in N,N-dimethylformamide (7 mL) was added sodium cyanate (412 mg, 8.41 mmol), and the mixture was stirred at 80° C. for 1 hr. The reaction mixture was diluted with a mixed solvent of ethyl acetate/hexane (1:1). The solution was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. The insoluble material was filtered off, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (ethyl acetate/hexane=2/98→20/80), and the fractions containing the object product were concentrated under reduced pressure. The obtained residue was recrystallized from ethyl acetate and hexane to give the title compound (470 mg, 79%) as white crystals. The solution was washed with water and saturated brine dried over anhydrous magnesium sulfate The insoluble material was filtered off the filtrate was concentrated under reduced pressure The obtained residue was purified by silica gel column chromatography (ethyl acetate/hexane=2/98→20/80) the fractions containing the object product were concentrated under reduced pressure The obtained residue was recrystallized from ethyl acetate and hexane

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of methyl 2-chloro-3-methylbenzoate (3.60 g, 19.4 mmol) in acetonitrile (60 mL) were added 1-bromopyrrolidine-2,5-dione (11.46 g, 64.3 mmol) and 2,2′-(E)-diazen-1,2-diylbis(2-methylpropanenitrile) (960 mg, 5.84 mmol), and the mixture was stirred at 90° C. for 26 hr. The insoluble material was filtered off from the reaction mixture, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate=100/0→95/5), and the fractions containing the object product were concentrated under reduced pressure to give the title compound (3.42 g, 66%) as a colorless oil. The insoluble material was filtered off from the reaction mixture the filtrate was concentrated under reduced pressure The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate=100/0→95/5) the fractions containing the object product were concentrated under reduced pressure

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

実験手順: To a solution of methyl 3-(bromomethyl)-2-chlorobenzoate (748 mg, 2.84 mmol) in N,N-dimethylformamide (7 mL) was added sodium cyanate (412 mg, 8.41 mmol), and the mixture was stirred at 80° C. for 1 hr. The reaction mixture was diluted with a mixed solvent of ethyl acetate/hexane (1:1). The solution was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. The insoluble material was filtered off, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (ethyl acetate/hexane=2/98→20/80), and the fractions containing the object product were concentrated under reduced pressure. The obtained residue was recrystallized from ethyl acetate and hexane to give the title compound (470 mg, 79%) as white crystals. The solution was washed with water and saturated brine dried over anhydrous magnesium sulfate The insoluble material was filtered off the filtrate was concentrated under reduced pressure The obtained residue was purified by silica gel column chromatography (ethyl acetate/hexane=2/98→20/80) the fractions containing the object product were concentrated under reduced pressure The obtained residue was recrystallized from ethyl acetate and hexane

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of methyl 2-chloro-3-methylbenzoate (3.60 g, 19.4 mmol) in acetonitrile (60 mL) were added 1-bromopyrrolidine-2,5-dione (11.46 g, 64.3 mmol) and 2,2′-(E)-diazen-1,2-diylbis(2-methylpropanenitrile) (960 mg, 5.84 mmol), and the mixture was stirred at 90° C. for 26 hr. The insoluble material was filtered off from the reaction mixture, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate=100/0→95/5), and the fractions containing the object product were concentrated under reduced pressure to give the title compound (3.42 g, 66%) as a colorless oil. The insoluble material was filtered off from the reaction mixture the filtrate was concentrated under reduced pressure The obtained residue was purified by silica gel column chromatography (hexane/ethyl acetate=100/0→95/5) the fractions containing the object product were concentrated under reduced pressure

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

実験手順: To a solution of methyl 3-(bromomethyl)-2-chlorobenzoate (748 mg, 2.84 mmol) in N,N-dimethylformamide (7 mL) was added sodium cyanate (412 mg, 8.41 mmol), and the mixture was stirred at 80° C. for 1 hr under nitrogen stream. The reaction mixture was diluted with a mixed solvent of ethyl acetate and hexane (1:1). The solution was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtrated. The solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (ethyl acetate/hexane=2/98→20/80), and recrystallized from ethyl acetate and hexane to give the title compound (470 mg, 79%) as white crystals. The solution was washed with water and saturated brine dried over anhydrous magnesium sulfate filtrated The solvent was evaporated under reduced pressure the obtained residue was purified by silica gel column chromatography (ethyl acetate/hexane=2/98→20/80) recrystallized from ethyl acetate and hexane

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of methyl 2-chloro-3-methylbenzoate (3.60 g, 19.4 mmol) in acetonitrile (60 mL) were added 1-bromopyrrolidine-2,5-dione (11.46 g, 64.3 mmol) and 2,2′-(E)-diazen-1,2-diylbis(2-methylpropanenitrile) (960 mg, 5.84 mmol), and the mixture was stirred at 90° C. for 26 hr. The reaction mixture was concentrated, the insoluble material was filtered off, and the filtrate was concentrated. The obtained residue was purified by silica gel column chromatography (ethyl acetate/hexane=0/100→5/95) to give the title compound (3.42 g, 66%) as a colorless oil. The reaction mixture was concentrated the insoluble material was filtered off the filtrate was concentrated The obtained residue was purified by silica gel column chromatography (ethyl acetate/hexane=0/100→5/95)