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

HRID 1258969Notes

Reaction equation

HRID 1258969 reaction equation
[C:1]([O:10]CC)(=[O:9])[C:2]1[C:3](=[CH:5][CH:6]=[CH:7][CH:8]=1)[OH:4].Br[CH2:14][C:15]([CH3:17])=[CH2:16].C(=O)([O-])[O-].[K+].[K+].[OH-].[Na+]>CC(=O)CC.CCO>[CH3:16][C:15](=[CH2:14])[CH2:17][O:4][C:3]1[CH:5]=[CH:6][CH:7]=[CH:8][C:2]=1[C:1]([OH:10])=[O:9]

Participants

7

Reactant 4

HCID 8365Ethyl SalicylateHCID 11430Potassium CarbonateHCID 14798Sodium HydroxideHCID 3577853-Bromo-2-methyl-1-propene

Product 1

HCID 111271062-[(2-Methylprop-2-en-1-yl)oxy]benzoic acidYield 91.2%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6569Methyl Ethyl KetoneSolvent

Conditions

Temperature
25 °C

Procedure

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.

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 48 h
  3. customthe suspended inorganic salt was removed by filtration
  4. customThe concentration of the resulting solution by rotary evaporation
  5. customyielded pale yellowish syrup, which
  6. customethanol was removed at reduced pressure
  7. customwas acidified by 6N HCl to pH 2 at 5° C.
  8. extractionthe mixture was extracted with Et2O (50 ml×3)
  9. washwashed with water (10 ml×2) respectively
  10. extractionThe ether extract
  11. dry with materialwas dried with anhydrous sodium sulfate
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-953c6b92b75a44338a68a08e24c52791
Source dataset
uspto-grants-2013_06
Patent number
US08466199B2

Reaction notes

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