(3,5-difluoro-4-formylphenyl) propan-2-yl carbonate

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

実験手順: To a 250 mL dry round bottom flask were added 2,6-difluoro-4-hydroxy-benzaldehyde (4.80 g, 30.4 mmol), anhydrous CH2Cl2 (30 mL) and pyridine (3.0 mL, 36.5 mmol). The mixture was stirred in an ice-water bath, then a solution of isopropyl chloroformate in toluene (1.0 M, 33.4 mL) was added. After stirring at 0° C. for 2 hours, the mixture was stirred at room temperature overnight. Water (80 mL) was added to the reaction mixture. The CH2Cl2 layer was separated, and the aqueous layer was extracted continually with CH2Cl2 (80 mL×3). The combined CH2Cl2 solution was dried over Na2SO4. After removal of the solvent, the residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting) to give 3,5-difluoro-4-formylphenyl isopropyl carbonate (6.20 g) as a colorless oil. Yield: 84%. 1H NMR (CDCl3, 300 MHz): δ=10.30 (s, 1H), 7.02-6.96 (m, 2H), 5.03 (seventet, J=6.3 Hz, 1H), 1.43 (d, J=6.3 Hz, 6H). 13C NMR (CDCl3, 75.5 MHz): δ=183.3, 163.6 (dd, J=262.5, 7.92 Hz), 156.3 (t, J=15.2 Hz), 151.1, 111.9 (t, J=11.5 Hz), 106.0 (dd, J=25.1, 3.62 Hz), 74.5, 21.5. 19F NMR (CDCl3, 282.3 MHz): δ=−113.0 (d, J=9.0 Hz). To a 250 mL dry round bottom flask After stirring at 0° C. for 2 hours the mixture was stirred at room temperature overnight The CH2Cl2 layer was separated the aqueous layer was extracted continually with CH2Cl2 (80 mL×3) The combined CH2Cl2 solution was dried over Na2SO4 After removal of the solvent the residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting)

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

実験手順: To a 250 mL dry round bottom flask were added 2,6-difluoro-4-hydroxy-benzaldehyde (4.80 g, 30.4 mmol), anhydrous CH2Cl2 (30 mL) and pyridine (3.0 mL, 36.5 mmol). The mixture was stirred in an ice-water bath, then a solution of isopropyl chloroformate in toluene (1.0 M, 33.4 mL) was added. After stirring at 0° C. for 2 hours, the mixture was stirred at room temperature overnight. Water (80 mL) was added to the reaction mixture. The CH2Cl2 layer was separated, and the aqueous layer was extracted continually with CH2Cl2 (80 mL×3). The combined CH2Cl2 solution was dried over Na2SO4. After removal of the solvent, the residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting) to give 3,5-difluoro-4-formylphenyl isopropyl carbonate (6.20 g) as a colorless oil. Yield: 84%. 1H NMR (CDCl3, 300 MHz): δ=10.30 (s, 1H), 7.02-6.96 (m, 2H), 5.03 (seventet, J=6.3 Hz, 1H), 1.43 (d, J=6.3 Hz, 6H). 13C NMR (CDCl3, 75.5 MHz): δ=183.3, 163.6 (dd, J=262.5, 7.92 Hz), 156.3 (t, J=15.2 Hz), 151.1, 111.9 (t, J=11.5 Hz), 106.0 (dd, J=25.1, 3.62 Hz), 74.5, 21.5. 19F NMR (CDCl3, 282.3 MHz): δ=−113.0 (d, J=9.0 Hz). To a 250 mL dry round bottom flask After stirring at 0° C. for 2 hours the mixture was stirred at room temperature overnight The CH2Cl2 layer was separated the aqueous layer was extracted continually with CH2Cl2 (80 mL×3) The combined CH2Cl2 solution was dried over Na2SO4 After removal of the solvent the residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting)

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

実験手順: To a 250 mL dry round bottom flask were added 2,6-difluoro-4-hydroxybenzaldehyde (4.80 g, 30.4 mmol), anhydrous CH2Cl2 (30 mL) and pyridine (3.0 mL, 36.5 mmol). The mixture was stirred in an ice-water bath, then a solution of isopropyl chloroformate in toluene (1.0 M, 33.4 mL) was added. After stirring at 0° C. for 2 hours, the mixture was stirred at room temperature overnight. Water (80 mL) was added to the reaction mixture. The CH2Cl2 layer was separated, and the aqueous layer was extracted continually with CH2Cl2 (80 mL×3). The combined CH2Cl2 solution was dried over Na2SO4. After removal of the solvent, the residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting) to give 3,5-difluoro-4-formylphenyl isopropyl carbonate (6.20 g) as a colorless oil. Yield: 84%. 1H NMR (CDCl3, 300 MHz): δ=10.30 (s, 1H), 7.02-6.96 (m, 2H), 5.03 (seventet, J=6.3 Hz, 1H), 1.43 (d, J=6.3 Hz, 6H). 13C NMR (CDCl3, 75.5 MHz): δ=183.3, 163.6 (dd, J=262.5, 7.92 Hz), 156.3 (t, J=15.2 Hz), 151.1, 111.9 (t, J=11.5 Hz), 106.0 (dd, J=25.1, 3.62 Hz), 74.5, 21.5. 19F NMR (CDCl3, 282.3 MHz): δ=−113.0 (d, J=9.0 Hz). To a 250 mL dry round bottom flask After stirring at 0° C. for 2 hours the mixture was stirred at room temperature overnight The CH2Cl2 layer was separated the aqueous layer was extracted continually with CH2Cl2 (80 mL×3) The combined CH2Cl2 solution was dried over Na2SO4 After removal of the solvent the residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting)