Furfural → HCID 67544376, compound

HRID 922438Notes

Reaction equation

HRID 922438 reaction equation
[H-].[Na+].C(OP([CH:11]([CH2:17][C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[C:12]([O:14][CH2:15][CH3:16])=[O:13])(OCC)=O)C.[O:25]1[CH:29]=[CH:28][CH:27]=[C:26]1[CH:30]=O>O1CCCC1>[O:25]1[CH:29]=[CH:28][CH:27]=[C:26]1/[CH:30]=[C:11](\[CH2:17][C:18]([O:20][C:21]([CH3:22])([CH3:23])[CH3:24])=[O:19])/[C:12]([O:14][CH2:15][CH3:16])=[O:13]

Participants

5

Reactant 3

HCID 7362FurfuralHCID 24758Sodium hydrideHCID 11121291HCID 11121291, compound

Product 1

HCID 67544376HCID 67544376, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a suspension of 60% oil-based sodium hydride (6.50 g) in tetrahydrofuran (400 mL) was added dropwise a solution of 4-tert-butyl 1-ethyl 2-(diethoxyphosphoryl)succinate (55.0 g) in tetrahydrofuran (100 mL) under ice-cooling over 30 minutes, and then the mixture was stirred under the cooling for 1 hour. Then, thereto was added a solution of 2-furaldehyde (12.8 mL) in tetrahydrofuran (40 mL) under ice-cooling over 15 minutes, and the mixture was stirred at room temperature for 1 hour. Ice water was poured into the reaction mixture under ice-cooling, and the mixture was extracted with ethyl acetate. The organic layer was sequentially washed with water and saturated saline, dried over sodium sulfate, and then concentrated under reduced pressure to give 4-tert-butyl 1-ethyl (2E)-2-(2-furylmethylene)succinate (47.0 g) as a brown oil crude. Then, the oil (47.0 g) was stirred in trifluoroacetic acid (100 mL) at room temperature for 1 hour, and then concentrated under reduced pressure. The resulting residue was treated azeotropically with toluene several times to give (3E)-3-(ethoxycarbonyl)-4-(2-furyl)-but-3-enoic acid (39.2 g) as a brown oil crude. Then, the oil (39.2 g) was dissolved in acetic anhydride (100 mL), and thereto was added potassium acetate (19.8 g), and then the mixture was heated to reflux for 45 minutes. The reaction mixture was let stand to be cooled, and then thereto was added water (100 mL), and then the mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over sodium sulfate, and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate=5/1) to give ethyl 4-(acetyloxy)benzofuran-6-carboxylate (24.7 g) as a pale orange solid. APCI-MS m/z: 266 [M+NH4]+.

Workup

  1. temperaturecooling over 30 minutes
  2. temperaturecooling over 15 minutes
  3. stirringthe mixture was stirred at room temperature for 1 hour
  4. temperaturecooling
  5. extractionthe mixture was extracted with ethyl acetate
  6. washThe organic layer was sequentially washed with water and saturated saline
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-0c1cb5a8dc644cea82adde7fa98d6e1f
Source dataset
uspto-grants-2016_03
Patent number
US09278944B2

Reaction notes

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