5-Methylfurfural → 3-(Ethoxycarbonyl)-4-(5-methyl-2-furyl)but-3-enoic Acid

HRID 1643726Notes

Reaction equation

HRID 1643726 reaction equation
CC[O-].[Na+].[CH3:5][C:6]1[O:10][C:9]([CH:11]=O)=[CH:8][CH:7]=1.[C:13]([O:22]CC)(=[O:21])[CH2:14][CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17]>C(O)C>[CH2:19]([O:18][C:16]([C:15](=[CH:11][C:9]1[O:10][C:6]([CH3:5])=[CH:7][CH:8]=1)[CH2:14][C:13]([OH:22])=[O:21])=[O:17])[CH3:20]

Participants

5

Reactant 3

HCID 120975-MethylfurfuralHCID 31249Diethyl SuccinateHCID 2723922Sodium ethoxide

Product 1

HCID 667559123-(Ethoxycarbonyl)-4-(5-methyl-2-furyl)but-3-enoic AcidYield 21%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Sodium ethylate (74.2 g, 1.09 mol) was added under vigorous stirring to a solution of 5-methyl-2-furaldehyde 1 (100 g, 0.91 mol) and diethyl succinate (316 g, 1.81 mol) in ethanol (1 L). The reaction mixture was refluxed for 8 h and evaporated in vacuum (˜20 mmHg) at 50° C. until the solvent distillation ceased. The obtained residue was diluted with 500 mL of 10% HCl and 500 mL of ethyl acetate. The mixture was shaken. The organic layer was separated, diluted with 500 mL of a saturated aqueous solution of NaHCO3, and shaken. The aqueous layer was separated, acidified with 10% HCl to pH 2, and subjected to extraction with 1 L of ethyl acetate. The organic layer was evaporated in vacuum (˜20 mmHg) at 60° C. and chromatographed on a layer of silica gel (200×150 mm) with hexane/ethyl acetate mixture, 1:1 as eluent. Fractions with the target product were collected and evaporated in vacuum to give 45 g (0.19 mol, 21%) of the desired compound as a yellow solid.

Workup

  1. temperatureThe reaction mixture was refluxed for 8 h
  2. customevaporated in vacuum (˜20 mmHg) at 50° C. until the solvent distillation
  3. additionThe obtained residue was diluted with 500 mL of 10% HCl and 500 mL of ethyl acetate
  4. customThe organic layer was separated
  5. additiondiluted with 500 mL of a saturated aqueous solution of NaHCO3
  6. stirringshaken
  7. customThe aqueous layer was separated
  8. extractionsubjected to extraction with 1 L of ethyl acetate
  9. customThe organic layer was evaporated in vacuum (˜20 mmHg) at 60° C.
  10. customchromatographed on a layer of silica gel (200×150 mm) with hexane/ethyl acetate mixture, 1:1 as eluent
  11. customFractions with the target product were collected
  12. customevaporated in vacuum

Sources & evidence

ORD record
ord-703bdad79d7b47328dc495e4f1b59a7e
Source dataset
uspto-grants-2012_02
Patent number
US08119624B2

Reaction notes

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