Reaction #155421

Reaction equation

N2

4-hydroxybenzaldehyde

pyridine

ethyl chloroformate

→

ethyl 4-formylphenyl carbonate

Yield 92.0%

Solvents

CH2Cl2

water

Conditions

Workup

1. 1
   OtherTo a 250 mL dry round bottom flask
2. 2
   TemperatureThe solution was cooled in an ice-water bath
3. 3
   workup.STIRRINGThe mixture was stirred
4. 4
   workup.STIRRINGstirred at room temperature overnight
5. 5
   Otherthe CH2Cl2 layer was separated
6. 6
   ExtractionThe aqueous layer was extracted continually with CH2Cl2 (100 mL×2)
7. 7
   DryingThe combined CH2Cl2 solution was dried over Na2SO4
8. 8
   OtherAfter removal of the solvent
9. 9
   Otherthe residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting)

Procedure

To a 250 mL dry round bottom flask were added 4-hydroxybenzaldehyde (6.11 g, 50.0 mmol), anhydrous CH2Cl2 (150 mL). The solution was cooled in an ice-water bath, then pyridine (4.86 mL, 60.0 mmol) was added. To the resulting solution, ethyl chloroformate (4.78 mL, 50.0 mmol) was added slowly under stirring and N2. The mixture was stirred and warmed to room temperature, then stirred at room temperature overnight. To the reaction mixture, water (100 mL) was added and the CH2Cl2 layer was separated. The aqueous layer was extracted continually with CH2Cl2 (100 mL×2). 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 ethyl 4-formylphenyl carbonate (8.92 g) as colorless oil. Yield: 92%. 1H NMR (CDCl3, 300 MHz): δ=10.07 (s, 1H), 8.00 (d, J=8.7 Hz, 2H), 7.45 (d, J=8.7 Hz, 2H), 4.42 (q, J=7.2 Hz, 2H), 1.47 (t, J=7.2 Hz, 3H). 13C NMR (CDCl3, 75.5 MHz): δ=191.0, 155.7, 152.9, 134.2, 131.4, 121.9, 65.4, 14.3.

Source