Carbon Dioxide → 5-Methoxythiophene-2-carboxylic acid

HRID 1961240Notes

Reaction equation

HRID 1961240 reaction equation
[CH3:1][O:2][C:3]1[S:4][CH:5]=[CH:6][CH:7]=1.[Li]CCCC.[C:13](=[O:15])=[O:14]>O1CCCC1>[CH3:1][O:2][C:3]1[S:4][C:5]([C:13]([OH:15])=[O:14])=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 280Carbon DioxideHCID 856102-MethoxythiopheneHCID 178418339Butyllithium

Product 1

HCID 51881195-Methoxythiophene-2-carboxylic acidYield 91%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

2-(methyloxy)thiophene (1.01 g, 8.85 mmol) was added slowly over 15 min to a 100 mL round-bottomed flask containing 2.5M nBuLi in hexanes (3.8 mL, 9.50 mmol) in Tetrahydrofuran (THF) (40 mL) at −78° C. After warming to room temperature and stirring for 2 h, the mixture was cooled to −35° C. and crushed solid CO2 was added. The mixture warmed to room temperature over 3 hours and was cooled in an ice bath and quenched with NH4Cl(sat.). The cold reaction mixture was partitioned between CHCl3/H2O, the aqueous layer was made acidic with 6N HCl. The separated organic layer was dried with Na2SO4 and concentrated affording the title compound (1.3 g, 8.05 mmol, 91%) which was used without further purification: LC-MS (ES) m/z=159 (M+H)+.

Workup

  1. temperaturethe mixture was cooled to −35° C.
  2. additionwas added
  3. temperatureThe mixture warmed to room temperature over 3 hours
  4. temperaturewas cooled in an ice bath
  5. customquenched with NH4Cl(sat.)
  6. customThe cold reaction mixture
  7. customwas partitioned between CHCl3/H2O
  8. dry with materialThe separated organic layer was dried with Na2SO4
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-d2e9ebf6f3d346d8b3155c32a18d6742
Source dataset
uspto-grants-2013_04
Patent number
US08410158B2

Reaction notes

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