Carbon Dioxide → 5-tert-butylfuran-2-carboxylic Acid

HRID 635240

Reaction equation

HRID 635240 reaction equation
C([Li])CCC.[C:6]([C:10]1[O:11][CH:12]=[CH:13][CH:14]=1)([CH3:9])([CH3:8])[CH3:7].[C:15](=[O:17])=[O:16]>C1COCC1>[C:6]([C:10]1[O:11][C:12]([C:15]([OH:17])=[O:16])=[CH:13][CH:14]=1)([CH3:9])([CH3:8])[CH3:7]

Participants

5

Reactant 3

HCID 280Carbon Dioxide2×HCID 1389032-tert-ButylfuranHCID 178418339Butyllithium

Product 1

HCID 45190505-tert-butylfuran-2-carboxylic AcidYield 69%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

n-Butyllithium (25 mL, 40 mmol, 1.6 M in hexane solution, 1.1 equiv) is added dropwise to a solution of 4.5 g of 2-t-butylfuran (36 mmol) in 60 mL of dry THF at −78° C. under N2. After 30 min, the cooling bath is replaced with an ice bath and the mixture stirred at 0° C. for 1 h. Dry CO2, generated from dry ice and dried over an anhydrous Na2SO4 tower, is bubbled into the reaction mixture over 20 min at −78° C. and then at 0° C. The reaction mixture is acidified with 1 M HCl to pH 1, then extracted with ethyl acetate. The organic layer is washed with brine, dried (NaSO4) and concentrated to give 4.2 g of 2-tertbutyl 5-furanoic acid as a pale yellow solid (69%). 1H NMR (CDCl3) d 11.0 (br s, 1H), 7.19 (d, 1H, J=3.3 Hz), 6.11 (d 1H, J=3.3 Hz), 1.29 (s, 9H).

Workup

  1. customthe cooling bath is replaced with an ice bath
  2. dry with materialdried over an anhydrous Na2SO4 tower
  3. customis bubbled into the reaction mixture over 20 min at −78° C.
  4. customat 0° C
  5. extractionextracted with ethyl acetate
  6. washThe organic layer is washed with brine
  7. dry with materialdried (NaSO4)
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-4a3445da851f4843bc3a9a1ac7602e65
Source dataset
uspto-grants-2001_02
Patent number
US06187799B1

Linked notes

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