Hydrochloric Acid → Methyl 2-acetyl-3,5-dihydroxyphenylacetate

HRID 495184Notes

Reaction equation

HRID 495184 reaction equation
[C:1]([C:4]1[C:9]([O:10]CC=C)=[CH:8][C:7]([O:14]CC=C)=[CH:6][C:5]=1[CH2:18][C:19]([O:21][CH3:22])=[O:20])(=[O:3])[CH3:2].C([O-])=O.[NH4+].Cl>O1CCOCC1.CC1C=CC=CC=1[P](C1C=CC=CC=1C)([Pd][P](C1=C(C)C=CC=C1)(C1C=CC=CC=1C)C1C=CC=CC=1C)C1C=CC=CC=1C>[C:1]([C:4]1[C:9]([OH:10])=[CH:8][C:7]([OH:14])=[CH:6][C:5]=1[CH2:18][C:19]([O:21][CH3:22])=[O:20])(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 2723923Ammonium formateHCID 68421776Methyl 2-acetyl-3,5-diallyloxyphenylacetate

Product 1

HCID 15470976Methyl 2-acetyl-3,5-dihydroxyphenylacetateYield 39%

Reagents, catalysts & solvents 2

HCID 178424408HCID 178424408, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

Methyl 2-acetyl-3,5-diallyloxyphenylacetate (22 g, 72 mmol) obtained in Example 5, Step 2 was dissolved in 1,4-dioxane (0.20 L). To the solution were added ammonium formate (18 g, 0.29 mol) and bis(triphenylphosphine)palladium (II) dichloride (2.5 g, 3.6 mmol), followed by stirring for 8 hours under heating and reflux. After cooling to room temperature, the reaction mixture was made acidic by addition of 3 mol/L hydrochloric acid (0.20 L) and then concentrated under reduced pressure. The resulting residue was extracted with a mixed solvent of ethyl acetate and methanol (ethyl acetate/methanol=4/1, 0.20 L×4). The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (ethyl acetate/hexane=1/2) to obtain methyl 2-acetyl-3,5-dihydroxyphenylacetate (6.2 g, 39%).

Workup

  1. temperatureunder heating
  2. temperaturereflux
  3. concentrationconcentrated under reduced pressure
  4. extractionThe resulting residue was extracted with a mixed solvent of ethyl acetate and methanol (ethyl acetate/methanol=4/1, 0.20 L×4)
  5. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe resulting residue was purified by silica gel column chromatography (ethyl acetate/hexane=1/2)

Sources & evidence

ORD record
ord-c426a3eb970e48a08a8614b6b369041f
Source dataset
uspto-grants-2009_05
Patent number
US07538224B2

Reaction notes

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