Réaction #155430

Équation de réaction

chloromethyl butyrate

2-fluoro-4-hydroxybenzaldehyde

K2CO3

→

(3-fluoro-4-formylphenoxy)methyl butyrate

Rendement 66.6%

Solvants

acetone

acetone

acetone

Conditions de réaction

Traitement

1. 1
   AutreTo a 500 mL dry round bottom flask
2. 2
   AutreTo another 500 mL dry round bottom flash b
3. 3
   workup.STIRRINGThis mixture was also stirred at room temperature for 30 minutes
4. 4
   Autrewas decanted into the stirring solution in the round bottom flask a
5. 5
   TempératureThe resulting mixture was refluxed for 4 hours
6. 6
   Autrethe residual solid was triturated with methyl tert-butyl ether (MTBE) three times (100 mL, 50 mL, 50 mL)
7. 7
   ExtractionThe MTBE extract
8. 8
   Concentrationwas concentrated
9. 9
   Autrethe residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting)

Mode opératoire

To a 500 mL dry round bottom flask a were added 2-fluoro-4-hydroxybenzaldehyde (5.60 g, 40 mmol), anhydrous K2CO3 (10.6 g, 76.9 mmol) and acetone (200 mL). The mixture was stirred at room temperature for 30 minutes. To another 500 mL dry round bottom flash b were added chloromethyl butyrate (9.33 g, 61.5 mmol), KI (14.2 g, 66.6 mmol) and acetone (150 mL). This mixture was also stirred at room temperature for 30 minutes. After the solid settled down on the glassware bottom, the top yellow acetone solution in flask b was decanted into the stirring solution in the round bottom flask a. The resulting mixture was refluxed for 4 hours. Most acetone was rotary evaporated, and the residual solid was triturated with methyl tert-butyl ether (MTBE) three times (100 mL, 50 mL, 50 mL). The MTBE extract was concentrated, and the residue was purified with a silica gel chromatography (heptane/ethyl acetate, gradient eluting) to give (3-fluoro-4-formylphenoxy)methyl butyrate (6.40 g) as a colorless oil. Yield: 43%. 1H NMR (CDCl3, 300 MHz): δ=10.18 (s, 1H), 7.80 (t, J=8.7 Hz, 1H), 6.93-6.89 (m, 1H), 6.82 (dd, J=12.3, 2.1 Hz, 1H), 5.83 (s, 2H), 2.36 (t, J=7.5 Hz, 2H), 1.64 (sextet, J=7.5 Hz, 2H), 0.92 (t, J=7.5 Hz, 3H). 13C NMR (CDCl3, 75.5 MHz): δ=185.5 (d, J=6.1 Hz), 169.7 (d, J=258.8 Hz), 162.8 (d, J=12.2 Hz), 130.2 (d, J=3.7 Hz), 119.1 (d, J=8.5Hz), 112.4 (d, J=3.1 Hz), 103.5 (d, J=24.4 Hz), 84.1, 35.7, 18.0, 13.3.

Source