Isoeugenol → Guaiacylacetone

HRID 1074643Notes

Reaction equation

HRID 1074643 reaction equation
[C:1]1([O:11][CH3:12])[C:2](=[CH:4][CH:5]=[C:6]([CH:10]=1)[CH:7]=[CH:8][CH3:9])[OH:3].C(OC(=O)C)(=[O:15])C.C([O-])(=O)C.[Na+].S(=O)(O)[O-].[Na+]>C(O)(=O)C.C1(C)C=CC=CC=1>[CH3:9][C:8]([CH2:7][C:6]1[CH:5]=[CH:4][C:2]([OH:3])=[C:1]([O:11][CH3:12])[CH:10]=1)=[O:15]

Participants

7

Reactant 4

HCID 7338IsoeugenolHCID 7918Acetic AnhydrideHCID 517045Sodium Acetate2×HCID 23665763Sodium Bisulfite

Product 1

HCID 17262GuaiacylacetoneYield 85.3%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 1140TolueneSolvent

Conditions

Temperature
20 °C

Procedure

A mixture of isoeugenol (8.21 g., 50 mm.), acetic anhydride (5.62 g., 55 mm.) and anhydrous sodium acetate (0.41 g., 5 mm.) is heated at 100° C.-105° C. under nitrogen atmosphere for 2.5 hours. The reaction mixture is cooled and diluted with 65 ml. of toluene before a solution (11 ml.) of 38.6% peracetic and 0.85 g. of sodium acetate in acetic acid is added slowly. After heating at 50° C.-60° C. for 2-3 hours, the reaction mixture is cooled to 20° C. and treated with aqueous sodium bisulfite (2.8 g.) to destroy excess peracetic acid. The entire mixture is mixed with 8 ml. of toluene, 50 ml. of 14% aqueous sulfuric acid, and is heated with stirring to reflux for 12.5 hours. After cooling to ambient temperature, the toluene layer is separated, and the aqueous layer extracted 3×20 ml. of toluene. The toluene layers are combined, washed with saturated aqueous sodium sulfate, dried over anhydrous magnesium sulfate and concentrated in vacuo to give methylvanillyl ketone in 85.3% yield.

Workup

  1. temperatureis heated at 100° C.-105° C. under nitrogen atmosphere for 2.5 hours
  2. temperatureThe reaction mixture is cooled
  3. additiondiluted with 65 ml
  4. temperatureAfter heating at 50° C.-60° C. for 2-3 hours
  5. customto destroy excess peracetic acid
  6. additionThe entire mixture is mixed with 8 ml
  7. temperatureof 14% aqueous sulfuric acid, and is heated
  8. temperatureto reflux for 12.5 hours
  9. temperatureAfter cooling to ambient temperature
  10. customthe toluene layer is separated
  11. extractionthe aqueous layer extracted 3×20 ml
  12. washwashed with saturated aqueous sodium sulfate
  13. dry with materialdried over anhydrous magnesium sulfate
  14. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-f9e6d09a9a7941d58ef376d3f6038a86
Source dataset
uspto-grants-1983_07
Patent number
US04393242

Reaction notes

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