Furfural → Ethyl 2-furanpropionate

HRID 1911302Notes

Reaction equation

HRID 1911302 reaction equation
C1(P(C2C=CC=CC=2)(C2C=CC=CC=2)=CC(OCC)=O)C=CC=CC=1.O1C=CC=C1C=O.[O:33]1[CH:37]=[CH:36][CH:35]=[C:34]1/[CH:38]=[CH:39]/[C:40]([O:42][CH2:43][CH3:44])=[O:41]>C1COCC1.C(O)C.[Pd]>[O:33]1[CH:37]=[CH:36][CH:35]=[C:34]1[CH2:38][CH2:39][C:40]([O:42][CH2:43][CH3:44])=[O:41]

Participants

7

Reactant 3

HCID 7362FurfuralHCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl esterHCID 699489(E)-Ethyl 3-(2-furyl)acrylate2×

Product 1

HCID 61450Ethyl 2-furanpropionate

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalyst2×HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of ethyl 2-triphenylphosphoranylideneacetate (34.84 g, 100 mmol, 1 eq) and furan-2-carbaldehyde (9609 mg, 100 mmol, 1 eq) in anhydrous THF (200 ml) was stirred at room temperature for 24 h. The solvent was evaporated under reduced pressure and the residue triturated with ether to produce a brown solution and a precipitate. The solid was filtered, washed and removed. The filtrate was then evaporated. The product was purified by column chromatography on silica eluting with 0-20% ethyl acetate in hexanes. The desired fractions were evaporated to yield a cis/trans mixture of ethyl (E)-3-(2-furyl)prop-2-enoate as a pale yellow oil (NMR suggested mainly trans product) (15.5 g, 93%). b) A cis/trans mixture of ethyl (E)-3-(2-furyl)prop-2-enoate (15.5 g, 93.27 mmol, 1 eq) was stirred in ethanol (120 ml) containing 10% palladium on charcoal (775 mg, 5% by w). The reaction mixture was stirred under hydrogen for 4 h. A further quantity of 10% Pd/C (775 mg, 5% by w) was added. The reaction was stirred under hydrogen for an additional 95 mins. The reaction was filtered and evaporated under reduced pressure. The crude product was purified by silica column chromatography eluting with 20% ethyl acetate in hexanes. The desired fractions were evaporated under reduced pressure and ethyl 3-(2-furyl)propanoate was obtained as a clear oil (3.69 g, 24% yield).

Workup

  1. customThe solvent was evaporated under reduced pressure
  2. customthe residue triturated with ether
  3. customto produce a brown solution
  4. filtrationThe solid was filtered
  5. washwashed
  6. customremoved
  7. customThe filtrate was then evaporated
  8. customThe product was purified by column chromatography on silica eluting with 0-20% ethyl acetate in hexanes
  9. customThe desired fractions were evaporated
  10. customto yield
  11. stirringThe reaction mixture was stirred under hydrogen for 4 h
  12. stirringThe reaction was stirred under hydrogen for an additional 95 mins
  13. filtrationThe reaction was filtered
  14. customevaporated under reduced pressure
  15. customThe crude product was purified by silica column chromatography
  16. washeluting with 20% ethyl acetate in hexanes
  17. customThe desired fractions were evaporated under reduced pressure

Sources & evidence

ORD record
ord-3de916c5edce4d24b5733d68bab94143
Source dataset
uspto-grants-2013_12
Patent number
US08604022B2

Reaction notes

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