Reaktion #1346150

Reaktionsgleichung

ethyl 2-hydroxy-6-methyl-benzoate

allyl bromide

potassium carbonate

NaOH

→

2-Allyloxy-6-methyl-benzoic acid

Ausbeute 83.2%

Lösungsmittel

2-Butanone

EtOH

Reaktionsbedingungen

Aufarbeitung

1. 1
   Temperaturwas heated
2. 2
   Temperaturto reflux for 48 h
3. 3
   Sonstigethe suspended inorganic salt was removed by filtration
4. 4
   SonstigeThe concentration of the resulting solution by rotary evaporation
5. 5
   Sonstigeyielded pale yellowish syrup, which
6. 6
   Sonstigeethanol was removed at reduced pressure
7. 7
   Sonstigewas acidified by 6N HCl to pH 2 at 5° C.
8. 8
   Extraktionthe mixture was extracted with Et2O (50 ml×3)
9. 9
   Waschenwashed with water (10 ml×2) respectively
10. 10
    ExtraktionThe ether extract
11. 11
    Trocknenwas dried with anhydrous sodium sulfate
12. 12
    Einengenconcentrated

Vorschrift

Under N2, the mixture of ethyl 2-hydroxy-6-methyl-benzoate (5.00 g, 27.75 mmol), allyl bromide (5.08 g, 3.55 ml, 42.00 mmol) and potassium carbonate (4.42 g, 32.00 mmol) in dry 2-Butanone (100 ml) was heated to reflux for 48 h. After the reaction mixture cooled down to 25° C., the suspended inorganic salt was removed by filtration. The concentration of the resulting solution by rotary evaporation yielded pale yellowish syrup, which was then mixed with 2N NaOH (20 ml, 40 mmol) and EtOH (30 ml). After this mixture was stirred for 48 h at 80° C., ethanol was removed at reduced pressure. After the aqueous solution was acidified by 6N HCl to pH 2 at 5° C., the mixture was extracted with Et2O (50 ml×3). The organic phase was combined and washed with water (10 ml×2) respectively. The ether extract was dried with anhydrous sodium sulfate and then concentrated to give 2-Allyloxy-6-methyl-benzoic acid as oil (4.44 g, 23.10 mmol). The title compound was then treated with of 1M sodium trimethylsilanolate (21.0 ml, 21.0 mmol) to give sodium 2-allyloxy-6-methyl-benzoate (4.65 g) as white powder. 1H-NMR (400 MHz, D2O): 7.06 (m, 1 arom. H); 6.73 (m, 2 arom. H); 5.92 (m, —CH═CH2); 5.29, 5.14 (2 d-like, CH═CH2); 4.47 (d-like, CH2—CH═CH2); 2.10 (s, —CH3). 13C-NMR (100 MHz, D2O): 176.86 (CO);=153.10; 134.09; 133.61; 131.33; 127.99; 122.84; 117.22; 110.91; 69.60; 18.36.

Quelle