Malonic Acid → 4-Vinylguaiacol

HRID 1021071Notes

Reaction equation

HRID 1021071 reaction equation
[OH:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=O)=[CH:4][C:3]=1[O:10][CH3:11].[C:12](O)(=O)CC(O)=O.N1CCCCC1.O>CN(C=O)C>[OH:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[CH2:12])=[CH:4][C:3]=1[O:10][CH3:11]

Participants

6

Reactant 4

HCID 867Malonic AcidHCID 962WaterHCID 1183VanillinHCID 8082Piperidine

Product 1

HCID 3324-VinylguaiacolYield 51%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture of 4-hydroxy-3-methoxybenzaldehyde (3.42 mmol), malonic acid (13.68 mmol), piperidine (15.58 mmol) in DMF (20 ml) were taken in a 100 ml round bottom flask fitted with a condenser. The flask was shaken well and placed inside the monomode microwave oven and irradiated (250 W, 160° C.) for 15 minutes in parts. After completion, the reaction mixture was poured in ice cooled water and extracted with ethyl acetate. The organic layer was washed with dil. HCl, brine and water and dried over sodium sulphate. The solvent was evaporated under reduced pressure to obtain liquid which was purified on silica gel by column chromatography using a mixture of hexane and ethyl acetate (9:1 to 6:4), provided 4-hydroxy-3-methoxystyrene, a sweet and pleasant smelling liquid, in 51% yield; 1H NMR (CDCl3) 7.36 (21-1, d), 6.94 (2H, m), 6.83 (5H, m), 5.59 (1H, s), 3.86 (3H, s), 3.75 (3H, s); 13C NMR (CDCl3) 159.0, 146.7, 145.2, 130.3, 127.4, 126.6, 126.1, 120.1, 114.5, 114.1, 108.0, 55.9 and 55.3.

Workup

  1. customwere taken in a 100 ml round bottom flask
  2. customfitted with a condenser
  3. customirradiated (250 W, 160° C.) for 15 minutes in parts
  4. additionAfter completion, the reaction mixture was poured in ice
  5. extractionextracted with ethyl acetate
  6. washThe organic layer was washed with dil. HCl, brine and water
  7. dry with materialdried over sodium sulphate
  8. customThe solvent was evaporated under reduced pressure
  9. customto obtain liquid which
  10. customwas purified on silica gel by column chromatography
  11. additiona mixture of hexane and ethyl acetate (9:1 to 6:4)

Sources & evidence

ORD record
ord-a5c7eb8c786d46f6a234568efdfe64dd
Source dataset
uspto-grants-2014_05
Patent number
US08716532B2

Reaction notes

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