Vanillin → Ethyl (4-formyl-2-methoxyphenoxy)acetate

HRID 2308319Notes

Reaction equation

HRID 2308319 reaction equation
[O:1]=[CH:2][C:3]1[CH:11]=[CH:10][C:8]([OH:9])=[C:5]([O:6][CH3:7])[CH:4]=1.Br[CH2:13][C:14]([O:16][CH2:17][CH3:18])=[O:15].C(=O)([O-])[O-].[K+].[K+]>CC(C)=O>[CH2:17]([O:16][C:14](=[O:15])[CH2:13][O:9][C:8]1[CH:10]=[CH:11][C:3]([CH:2]=[O:1])=[CH:4][C:5]=1[O:6][CH3:7])[CH3:18]

Participants

5

Reactant 3

HCID 1183VanillinHCID 7748Ethyl bromoacetateHCID 11430Potassium Carbonate

Product 1

HCID 968872Ethyl (4-formyl-2-methoxyphenoxy)acetate

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent2×

Procedure

A flask containing vanillin (20 g, 0.13 mol), ethyl bromoacetate (28.4 g, 0.17 mol) and potassium carbonate (32.7 g, 0.24 mol) and acetone 200 mL were heated to reflux for 3 hours. The reaction was allowed to come to rt. The acetone was stripped off and the residue partitioned between water and ethyl acetate. The ethyl acetate was washed with brine and dried over magnesium sulfate. The organic layer was concentrated and the solid triturated with hexanes to yield 28.4 grams of Example No. 169. Mp=56-59° C.; 1H NMR (DMSO) 9.83 (s, 1H), 7.50 (dd, 1H, J=2.0 Hz, 8.3 Hz), 7.42 (d, 1H, J=1.7 Hz,), 7.07 (d, 1H, J=8.4 Hz), 4.91 (s, 2H), 4.16 (q, 2H, J=7.2 Hz), 3.84 (s, 3H), 1.20 (t, 3H, J=7.1 Hz); MS eI m/z 238 (M+); CHN calcd for C12H14O5.

Workup

  1. temperaturewere heated
  2. temperatureto reflux for 3 hours
  3. customto come to rt
  4. customthe residue partitioned between water and ethyl acetate
  5. washThe ethyl acetate was washed with brine
  6. dry with materialdried over magnesium sulfate
  7. concentrationThe organic layer was concentrated
  8. customthe solid triturated with hexanes
  9. customto yield 28.4 grams of Example No

Sources & evidence

ORD record
ord-8cc59eeb7b90403794c5514e788d4dc8
Source dataset
uspto-grants-2004_12
Patent number
US06835729B2

Reaction notes

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