Dimethyl Carbonate → 2-Methyl-4-(2-propen-1-yloxy)benzoic acid

Participants

Reaction Conditions

Reaction Steps

To a solution of 4-allyloxy-1-bromo-2-methyl-benzene (10.87 g, 47.9 mmol) in THF (125 mL), a solution of n-butyl lithium (45 mL, 1.5 M in diethyl ether) is added at −75° C. The mixture is stirred at −75° C. for 30 min before it is transferred via a double-tip needle into a cooled (0° C.) solution of dimethylcarbonate (12.93 g, 144 mmol) in THF (45 mL). The mixture is stirred at 0° C. for 2 h, then at rt for 20 h before the solvents are removed in vacuo. The remaining oil is evaporated twice from ethanol (100 mL) before it is dissolved in 2 M aq. LiOH solution (75 mL) and ethanol (100 mL). The mixture is stirred at rt for 2 days and at 60° C. for 1 h. The org. solvent is evaporated and the remaining solution is diluted with 0.5 M aq. NaOH solution and extracted with diethyl ether (100 mL). The org. extract is washed with 1 M aq. NaOH solution (150 mL). The combined basic aq. extracts are washed with diethyl ether (100 mL), acidified with 25% aq. HCl and extracted with DCM (2×100 mL). The DCM extracts are combined, dried over MgSO4, filtered, concentrated and dried under high vacuum to give 4-allyloxy-2-methyl-benzoic acid (5.83 g) as an orange solid; LC-MS: tR=0.87 min; [M+1]+=not detectable; 1H NMR (CDCl3): δ 2.66 (s, 3H), 4.62 (dt, J=5.3, 1.5 Hz, 2H), 5.34 (dq, J=10.5, 1.5 Hz, 1H), 5.45 (dq, J=17.1, 1.5 Hz, 1H), 6.03-6.13 (m, 1H), 6.79-6.83 (m, 2H), 8.08 (d, J=9.5 Hz, 1H).

Provenance & Evidence