Potassium Carbonate → 5-Bromo-2-(1-ethoxycarbonyl-ethoxy)-benzoic acid methyl ester

HRID 402919Notes

Reaction equation

HRID 402919 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[C:8]([Br:10])[CH:7]=[CH:6][C:5]=1[OH:11].[CH2:13]([O:15][C:16](=[O:20])[CH:17](Br)[CH3:18])[CH3:14].C(=O)([O-])[O-].[K+].[K+]>CC(C)=O>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[C:8]([Br:10])[CH:7]=[CH:6][C:5]=1[O:11][CH:17]([C:16]([O:15][CH2:13][CH3:14])=[O:20])[CH3:18]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 77683Methyl 5-bromosalicylateHCID 79040Ethyl 2-bromopropionate

Product 1

HCID 591920375-Bromo-2-(1-ethoxycarbonyl-ethoxy)-benzoic acid methyl esterYield 100%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

A mixture of 5-bromo-2-hydroxy-benzoic acid methyl ester (25.0 g, 103 mmol), 2-bromo-propionic acid ethyl ester (18.6 g, 103 mmol) and potassium carbonate (50.2 g, 360 mmol) in acetone (500 mL) is heated under reflux for 24 h. The reaction mixture is filtered, and the filtrate concentrated by rotary evaporation. The residue is dissolved in dichloromethane and washed twice with water. The organic layer is dried over Na2SO4, filtered and concentrated at reduced pressure to afford the title compound as a colorless oil (34.1 g, 103 mmol, 100%). 1H NMR (400 MHz, CDCl3, 298 K): δ=7.91 (d, J=2.7 Hz, 1H), 7.49 (dd, J=8.8, 2.7 Hz, 1H), 6.75 (d, J=8.8 Hz, 1H), 4.71 (q, J=6.8 Hz, 1H), 4.20 (q, J=7.1 Hz, 2H), 3.88 (s, 3H), 1.65 (d, J=6.8 Hz, 3H), 1.23 (t, J=7.1 Hz, 3H). MS (ES+): 331 (M(C13H1579BrO5)+H)+.

Workup

  1. temperatureis heated
  2. temperatureunder reflux for 24 h
  3. filtrationThe reaction mixture is filtered
  4. concentrationthe filtrate concentrated by rotary evaporation
  5. dissolutionThe residue is dissolved in dichloromethane
  6. washwashed twice with water
  7. dry with materialThe organic layer is dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated at reduced pressure

Sources & evidence

ORD record
ord-2dda80b0f9d34ab591f96ef61db502f9
Source dataset
uspto-grants-2014_06
Patent number
US08742132B2

Reaction notes

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