Ethyl bromoacetate → Ethyl (2-formyl-4-methylphenoxy)acetate

HRID 1773224Notes

Reaction equation

HRID 1773224 reaction equation
[OH:1][C:2]1[CH:9]=[CH:8][C:7]([CH3:10])=[CH:6][C:3]=1[CH:4]=[O:5].C([O-])([O-])=O.[K+].[K+].Br[CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20]>CN(C=O)C>[CH:4]([C:3]1[CH:6]=[C:7]([CH3:10])[CH:8]=[CH:9][C:2]=1[O:1][CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])=[O:5]

Participants

5

Reactant 3

HCID 7748Ethyl bromoacetateHCID 11430Potassium CarbonateHCID 69184Benzaldehyde, 2-hydroxy-5-methyl-

Product 1

HCID 13157005Ethyl (2-formyl-4-methylphenoxy)acetateYield 76.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 2-hydroxy-5-methylbenzaldehyde (2 g, 14.69 mmol) in 22 mL of DMF was added K2CO3 (4.06 g, 29.4 mmol) under N2 at room temperature. After the mixture was stirred for 10 min, ethyl 2-bromoacetate (1.625 mL, 14.69 mmol) was added. The reaction mixture was stirred at room temperature overnight, and filtered through Celite to remove solids. The filtrate was concentrated under reduced pressure, and the resulting residue was purified by silica gel flash chromatography, 100% Heptane-20% Ethyl Acetate/80% Heptane, to give a white solid, ethyl 2-(2-formyl-4-methylphenoxy)acetate (2.5 g). LCMS retention time=1.19 minutes (LC method 3); MS (m+1)=222.9. 1H NMR (400 MHz, DMSO-d6) δ 1.20 (t, J=7.1 Hz, 3H), 2.28 (s, 3H), 4.17 (q, J=7.2 Hz, 2H), 4.95 (s, 2H), 7.08 (d, J=8.6 Hz, 1H), 7.45 (ddd, J=8.6, 2.5, 0.6 Hz, 1H), 7.51 (d, J=2.2 Hz, 1H), 10.41 (s, 1H).

Workup

  1. stirringThe reaction mixture was stirred at room temperature overnight
  2. filtrationfiltered through Celite
  3. customto remove solids
  4. concentrationThe filtrate was concentrated under reduced pressure
  5. customthe resulting residue was purified by silica gel flash chromatography, 100% Heptane-20% Ethyl Acetate/80% Heptane

Sources & evidence

ORD record
ord-daa75d7413cc444581635cac077a9887
Source dataset
uspto-grants-2016_02
Patent number
US09255093B2

Reaction notes

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