3469-06-5

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: Benzocyclobutenone (1.20 g) was added slowly to concentrated sulfuric acid (5 mL) at 0° C. with vigorous stirring. The mixture of concentrated sulfuric acid (1.0 mL) and nitric acid (70%, 1.05 g) was added at such a rate that the solution temperature remained at 10° C. After the completion of addition of nitrating solution, the reaction mixture was then poured into icey water (30 mL). The resulting mixture was filtered. The filtrate was neutralized with sodium carbonate powders and the water was then evaporated under vacuum. The residue was then extracted with methylene chloride (3×50 mL). After removal of methylene chloride, the pure product (3-nitrobenzocyclobutenone) was isolated from the residue by chromatography on silica gel: 55 mg; IR (KBr) 1349, 1525, 1772 cm-1 ; 1H NMR (200 MHz, CDCl3) 4.42 (s, 2H), 7.68 (m, 2H), 8.31 (m, 1H); MS (EI, m/e, relative intensity %) 164 (M+. +H, 2.5), 135 (M+. -CO, 10.3), 89 (135 -.NO2, 38). was added at such a rate that the solution temperature remained at 10° C After the completion of addition of nitrating solution The resulting mixture was filtered the water was then evaporated under vacuum The residue was then extracted with methylene chloride (3×50 mL) After removal of methylene chloride

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Benzocyclobutenone (3.0 g, 25.42 mmol) was added slowly to concentrated sulfuric acid (6 mL) at -5° C.-0° C. with vigorous stirring. The resulting solution was further cooled to -10° C. and the mixture of concentrated sulfuric acid (3 mL) and nitric acid (70%, d 1.42, 2.0 mL) was added at such a rate that the solution temperature remained between -10° C. and -5° C. After the completion of addition of nitrating solution, stirring continued for 10 min. The reaction mixture was then poured into an ice slurry (30 g of ice in 30 mL of water). The product which precipitated out as yellow solids from water was collected by suction filtration and washed with water twice, aqueous sodium carbonate solution (10%) twice, and water twice consecutively. The solid product was recrystallized from methanol to give white fine crystals: 3.44 g (83.1%); mp 126°-127° C.; IR (KBr) 1342, 1522, 1785 cm-1 ; 1H NMR (200 MHz, CDCl3) 4.16 (s, 2H), 7.95 (d, 1H), 8.22 (s, 1H), 8.51 (d, 1H); MS (EI, m/e, relative intensity %) 163 (M+., 99.3), 135 (M+. -CO, 39.3), 89 (135 -.NO2, 100). was added at such a rate that the solution temperature remained between -10° C. and -5° C After the completion of addition of nitrating solution The product which precipitated out as yellow solids from water was collected by suction filtration washed with water twice The solid product was recrystallized from methanol to give white fine crystals

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

実験手順: Benzocyclobutenone (1.20 g) was added slowly to concentrated sulfuric acid (5 mL) at 0° C. with vigorous stirring. The mixture of concentrated sulfuric acid (1.0 mL) and nitric acid (70%, 1.05 g) was added at such a rate that the solution temperature remained at 10° C. After the completion of addition of nitrating solution, the reaction mixture was then poured into icey water (30 mL). The resulting mixture was filtered. The filtrate was neutralized with sodium carbonate powders and the water was then evaporated under vacuum. The residue was then extracted with methylene chloride (3×50 mL). After removal of methylene chloride, the pure product (3-nitrobenzocyclobutenone) was isolated from the residue by chromatography on silica gel: 55 mg; IR (KBr) 1349, 1525, 1772 cm-1 ; 1H NMR (200 MHz, CDCl3) 4.42 (s, 2H), 7.68 (m, 2H), 8.31 (m, 1H); MS (EI, m/e, relative intensity %) 164 (M+. +H, 2.5), 135 (M+. -CO, 10.3), 89 (135 -.NO2, 38). was added at such a rate that the solution temperature remained at 10° C After the completion of addition of nitrating solution The resulting mixture was filtered the water was then evaporated under vacuum The residue was then extracted with methylene chloride (3×50 mL) After removal of methylene chloride

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Benzocyclobutenone (3.0 g, 25.42 mmol) was added slowly to concentrated sulfuric acid (6 mL) at -5° C.-0° C. with vigorous stirring. The resulting solution was further cooled to -10° C. and the mixture of concentrated sulfuric acid (3 mL) and nitric acid (70%, d 1.42, 2.0 mL) was added at such a rate that the solution temperature remained between -10° C. and -5° C. After the completion of addition of nitrating solution, stirring continued for 10 min. The reaction mixture was then poured into an ice slurry (30 g of ice in 30 mL of water). The product which precipitated out as yellow solids from water was collected by suction filtration and washed with water twice, aqueous sodium carbonate solution (10%) twice, and water twice consecutively. The solid product was recrystallized from methanol to give white fine crystals: 3.44 g (83.1%); mp 126°-127° C.; IR (KBr) 1342, 1522, 1785 cm-1 ; 1H NMR (200 MHz, CDCl3) 4.16 (s, 2H), 7.95 (d, 1H), 8.22 (s, 1H), 8.51 (d, 1H); MS (EI, m/e, relative intensity %) 163 (M+., 99.3), 135 (M+. -CO, 39.3), 89 (135 -.NO2, 100). was added at such a rate that the solution temperature remained between -10° C. and -5° C After the completion of addition of nitrating solution The product which precipitated out as yellow solids from water was collected by suction filtration washed with water twice The solid product was recrystallized from methanol to give white fine crystals

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Benzocyclobutenone (3.0 g, 25.42 mmol) was added slowly to concentrated sulfuric acid (6 mL) at -5° C.-0° C. with vigorous stirring. The resulting solution was further cooled to -10° C. and the mixture of concentrated sulfuric acid (3 mL) and nitric acid (70%, d 1.42, 2.0 mL) was added at such a rate that the solution temperature remained between -10° C. and -5° C. After the completion of addition of nitrating solution, stirring continued for 10 min. The reaction mixture was then poured into an ice slurry (30 g of ice in 30 mL of water). The product which precipitated out as yellow solids from water was collected by suction filtration and washed with water twice, aqueous sodium carbonate solution (10%) twice, and water twice consecutively. The solid product was recrystallized from methanol to give white fine crystals: 3.44 g (83.1%); mp 126°-127° C.; IR (KBr) 1342, 1522, 1785 cm-1 ; 1H NMR (200 MHz, CDCl3) 4.16 (s, 2H), 7.95 (d, 1H), 8.22 (s, 1H), 8.51 (d, 1H); MS (EI, m/e, relative intensity %) 163 (M+., 99.3), 135 (M+. -CO, 39.3), 89 (135 -.NO2, 100). was added at such a rate that the solution temperature remained between -10° C. and -5° C After the completion of addition of nitrating solution The product which precipitated out as yellow solids from water was collected by suction filtration washed with water twice The solid product was recrystallized from methanol to give white fine crystals

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: Benzocyclobutenone (2.36 g, 0.02mol) was added slowly to a strongly stirred chlorosulfuric acid (3 mL) in chloroform (10 mL) solution. After the addition was done, the reaction mixture was stirred for 5 hours. Then the chloroform was evaporated, and the residue was precipitated in water yielding fine pink crystals. m.p. 80° C.; IR (KBr, cm−1): 1762; UV (λmax, methanol) 272 nm. After the addition Then the chloroform was evaporated the residue was precipitated in water yielding fine pink crystals

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

実験手順: Benzocyclobutenone (1.20 g) was added slowly to concentrated sulfuric acid (5 mL) at 0° C. with vigorous stirring. The mixture of concentrated sulfuric acid (1.0 mL) and nitric acid (70%, 1.05 g) was added at such a rate that the solution temperature remained at 10° C. After the completion of addition of nitrating solution, the reaction mixture was then poured into icey water (30 mL). The resulting mixture was filtered. The filtrate was neutralized with sodium carbonate powders and the water was then evaporated under vacuum. The residue was then extracted with methylene chloride (3×50 mL). After removal of methylene chloride, the pure product (3-nitrobenzocyclobutenone) was isolated from the residue by chromatography on silica gel: 55 mg; IR (KBr) 1349, 1525, 1772 cm-1 ; 1H NMR (200 MHz, CDCl3) 4.42 (s, 2H), 7.68 (m, 2H), 8.31 (m, 1H); MS (EI, m/e, relative intensity %) 164 (M+. +H, 2.5), 135 (M+. -CO, 10.3), 89 (135 -.NO2, 38). was added at such a rate that the solution temperature remained at 10° C After the completion of addition of nitrating solution The resulting mixture was filtered the water was then evaporated under vacuum The residue was then extracted with methylene chloride (3×50 mL) After removal of methylene chloride

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Benzocyclobutenone (3.0 g, 25.42 mmol) was added slowly to concentrated sulfuric acid (6 mL) at -5° C.-0° C. with vigorous stirring. The resulting solution was further cooled to -10° C. and the mixture of concentrated sulfuric acid (3 mL) and nitric acid (70%, d 1.42, 2.0 mL) was added at such a rate that the solution temperature remained between -10° C. and -5° C. After the completion of addition of nitrating solution, stirring continued for 10 min. The reaction mixture was then poured into an ice slurry (30 g of ice in 30 mL of water). The product which precipitated out as yellow solids from water was collected by suction filtration and washed with water twice, aqueous sodium carbonate solution (10%) twice, and water twice consecutively. The solid product was recrystallized from methanol to give white fine crystals: 3.44 g (83.1%); mp 126°-127° C.; IR (KBr) 1342, 1522, 1785 cm-1 ; 1H NMR (200 MHz, CDCl3) 4.16 (s, 2H), 7.95 (d, 1H), 8.22 (s, 1H), 8.51 (d, 1H); MS (EI, m/e, relative intensity %) 163 (M+., 99.3), 135 (M+. -CO, 39.3), 89 (135 -.NO2, 100). was added at such a rate that the solution temperature remained between -10° C. and -5° C After the completion of addition of nitrating solution The product which precipitated out as yellow solids from water was collected by suction filtration washed with water twice The solid product was recrystallized from methanol to give white fine crystals