Ethyl Salicylate → 2-[(2-Methylprop-2-en-1-yl)oxy]benzoic acid

Participants

Reaction Conditions

Reaction Steps

Under N2, the mixture of ethyl salicylate (4.99 g, 4.40 ml, 30.0 mmol), 3-Bromo-2-methyl-propene (8.10 g, 6.1 ml, 60.00 mmol) and potassium carbonate (5.53 g, 40.0 mmol) in dry 2-Butanone (120 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 (23 ml, 46 mmol) and EtOH (30 ml). After this mixture was stirred for 2 h at 50° 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-(2-Methyl-allyloxy)-benzoic acid as oil (5.26 g, 27.36 mmol). The title compound was then treated with of 1M sodium trimethylsilanolate (24.5 ml, 24.5 mmol) to give sodium 2-(2-methyl-allyloxy)-benzoate (4.18 g) as white powder. 1H-NMR (400 MHz, D2O): 7.36 (m, 2 arom. H); 7.04 (m, 2 arom. H); 5.09, 5.01 (2 d-like, C(CH3)═CH2); 4.57 (d-like, CH2—C(CH3)═CH2); 1.80 C(CH3)═CH2). 13C-NMR (100 MHz, D2O): 176.51 (C═O); 154.32; 141.73; 129.94; 129.76; 127.84; 121.03; 113.98; 112.19; 72.09; 18.57.

Provenance & Evidence