* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With oxygen; cobalt(II) diacetate tetrahydrate; sodium hydroxide In ethylene glycol at 80℃; for 8 h;
General procedure: a mixture of substrate 1a(1 mmol), cobalt salt (n1molpercent) and NaOH (n2 equiv)in EG (5 mL) was stirred with O2 (1 atm) being bubbled, under 80 oCfor 8 h. Hydrochloric acid (10 mL, 2percent) and methyl tert-butyl ether (MTBE, 10 mL) were successively added to the reactionmixture. The organic layer was separated, and the aqueous phase was furtherextracted with MTBE(10 mL × 2). The combined organic phase was dried over anhydrous sodium sulfateand concentrated to give a residue, which was purified by column chromatographyon silica gel (eluents: petroleum ether/ethyl acetate, 10/1) to provide thedesired products 2a.
Reference：
[1] Tetrahedron Letters, 2014, vol. 55, # 8, p. 1406 - 1411
[2] Green Chemistry, 2014, vol. 16, # 5, p. 2807 - 2814
[3] Green Chemistry, 2014, vol. 16, # 3, p. 1248 - 1254
2
[ 405-05-0 ]
[ 185345-46-4 ]
Yield
Reaction Conditions
Operation in experiment
48%
at 45℃; for 26 h;
Intermediate 26. 3-bromo-5-fluoro-4-hydroxybenzaldehyde (26)26; [0198] To a solution of 3-fluoro-4-hydroxybenzaldehyde (2 g, 14.3 mmol, 1 eq, Oakwood Products, Inc., West Columbia, SC, USA) in acetic acid (60 mL), was added a solution of bromine(2.7 g, 17.0 mmol, 1.2 eq) in acetic acid(10 mL), and the mixture was stirred at 45 °C for 26 h. After concentration in vacuo, brine (50 mL) was added to the residue and the mixture was extracted with EtOAc(3 X 80 mL). The combined organic layers were dried (Na2SO4), concentrated in vacuo, and purified by reversed phase semi-preparative .HPLC to afford 1.5 g (48percent) of_3-bromo-5-fluoro-4- hydroxybenzaldehyde (26).
48%
With bromine In acetic acid at 45℃; for 26 h;
Intermediate 12: 3-bromo-5-fluoro-4-hydroxybenzaldehyde (12)12[0157] To a solution of 3-fluoro-4-hydroxybenzaldehyde (2 g, 14.3 mmol, 1 eq) in acetic acid (60 mL), was added a solution of bromine(2.7 g, 17.0 mmol, 1.2 eq) in acetic acid(10 mL), and the mixture was stirred at 45 °C for 26h. After concentration in vacuo, brine (50 mL) was added to the residue and the mixture was extracted with EtOAc(3 X 80 mL). The combined organic layers were dried (Na2SO4), concentrated in vacuo, and purified by reversed phase semi-preparative .HPLC to afford 1.5 g (48 percent) of_3-bromo-5-fluoro-4-hydroxybenzaldehyde (12).
Intermediate 26. 3-bromo-5-fluoro-4-hydroxybenzaldehyde (26)26; [0198] To a solution of 3-fluoro-4-hydroxybenzaldehyde (2 g, 14.3 mmol, 1 eq, Oakwood Products, Inc., West Columbia, SC, USA) in acetic acid (60 mL), was added a solution of bromine(2.7 g, 17.0 mmol, 1.2 eq) in acetic acid(10 mL), and the mixture was stirred at 45 C for 26 h. After concentration in vacuo, brine (50 mL) was added to the residue and the mixture was extracted with EtOAc(3 X 80 mL). The combined organic layers were dried (Na2SO4), concentrated in vacuo, and purified by reversed phase semi-preparative .HPLC to afford 1.5 g (48%) of_3-bromo-5-fluoro-4- hydroxybenzaldehyde (26).
48%
With bromine; In acetic acid; at 45.0℃; for 26.0h;
Intermediate 12: 3-bromo-5-fluoro-4-hydroxybenzaldehyde (12)12[0157] To a solution of 3-fluoro-4-hydroxybenzaldehyde (2 g, 14.3 mmol, 1 eq) in acetic acid (60 mL), was added a solution of bromine(2.7 g, 17.0 mmol, 1.2 eq) in acetic acid(10 mL), and the mixture was stirred at 45 C for 26h. After concentration in vacuo, brine (50 mL) was added to the residue and the mixture was extracted with EtOAc(3 X 80 mL). The combined organic layers were dried (Na2SO4), concentrated in vacuo, and purified by reversed phase semi-preparative .HPLC to afford 1.5 g (48 %) of_3-bromo-5-fluoro-4-hydroxybenzaldehyde (12).
With oxygen; cobalt(II) diacetate tetrahydrate; sodium hydroxide; In ethylene glycol; at 80.0℃; under 760.051 Torr; for 8.0h;
General procedure: a mixture of substrate 1a(1 mmol), cobalt salt (n1mol%) and NaOH (n2 equiv)in EG (5 mL) was stirred with O2 (1 atm) being bubbled, under 80 oCfor 8 h. Hydrochloric acid (10 mL, 2%) and methyl tert-butyl ether (MTBE, 10 mL) were successively added to the reactionmixture. The organic layer was separated, and the aqueous phase was furtherextracted with MTBE(10 mL × 2). The combined organic phase was dried over anhydrous sodium sulfateand concentrated to give a residue, which was purified by column chromatographyon silica gel (eluents: petroleum ether/ethyl acetate, 10/1) to provide thedesired products 2a.
3-(3-bromo-5-fluoro-4-methoxybenzylidene)-5-(furan-2-carbonyl)indolin-2-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
50%
With piperidine; In ethanol; at 80.0℃; for 16.0h;Inert atmosphere;
General procedure: Piperidine (8.7 muL, 0.088 mmol), 3,5-difluoro-4-hydroxybenzaldehyde (69.5 mg, 0.44 mmol) and S3 (100.0 mg, 0.44 mmol) were dissolved in EtOH (2.0 mL). The mixture was heated to 80 oC for 16 h. The orange solid was filtered and washed with 1N HCl and Et2O to afford 3 (114.0 mg, 70%, mixture of E/Z isomers).
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