Carbon Dioxide → HCID 18668992, compound

HRID 1058650Notes

Reaction equation

HRID 1058650 reaction equation
Br[C:2]1[S:6][C:5]([S:7][C:8]2[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][CH:9]=2)=[C:4]([CH:15]([O:18]C)OC)[CH:3]=1.C([Li])CCC.[C:25](=[O:27])=[O:26].[OH-].[Na+]>O1CCCC1.O>[Cl:14][C:11]1[CH:10]=[CH:9][C:8]([S:7][C:5]2[S:6][C:2]([C:25]([OH:27])=[O:26])=[CH:3][C:4]=2[CH:15]=[O:18])=[CH:13][CH:12]=1

Participants

7

Reactant 4

HCID 280Carbon DioxideHCID 14798Sodium HydroxideHCID 18668924HCID 18668924, compoundHCID 178418339Butyllithium

Product 1

HCID 18668992HCID 18668992, compoundYield 54%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

In an argon atmosphere, 5-bromo-2-(4-chlorophenylthio)-3-(dimethoxymethyl)thiophene (1.04 g, 2.75 mmol) was dissolved in tetrahydrofuran (15 mL) and the mixture was cooled to −78° C. n-Butyl lithium (1.6 mol/L hexane solution; 2.5 mL, 4.1 mmol) was added thereto, followed by stirring for 5 minutes. Dry ice (about 1 g) was added thereto, followed by stirring for 10 minutes. Water and 1 mol/L sodium hydroxide aqueous solution was added to the reaction liquid so that pH becomes 10, and the mixture was washed with ether. 1 mol/L Hydrochloric acid was added to the aqueous layer so that pH becomes 3, and the aqueous layer was extracted with ethyl acetate. The organic layer was washed with water and brine and then dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residue was dissolved in tetrahydrofuran (10 mL). 1 mol/L hydrochloric acid (2 mL) was added thereto, followed by stirring at room temperature for 2 hours. Water was added to the reaction liquid and the product was extracted with ethyl acetate. The organic layer was washed with water and brine, and then dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the residue was triturated with isopropyl ether to give 2-(4-chlorophenylthio)-3-formyl-5-thiophenecarboxylic acid (439 mg, 54%).

Workup

  1. additionwas added
  2. stirringby stirring for 10 minutes
  3. washthe mixture was washed with ether
  4. addition1 mol/L Hydrochloric acid was added to the aqueous layer so that pH
  5. extractionthe aqueous layer was extracted with ethyl acetate
  6. washThe organic layer was washed with water and brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. customthe solvent was evaporated under reduced pressure
  9. dissolutionThe residue was dissolved in tetrahydrofuran (10 mL)
  10. addition1 mol/L hydrochloric acid (2 mL) was added
  11. stirringby stirring at room temperature for 2 hours
  12. additionWater was added to the reaction liquid
  13. extractionthe product was extracted with ethyl acetate
  14. washThe organic layer was washed with water and brine
  15. dry with materialdried over anhydrous sodium sulfate
  16. customThe solvent was evaporated under reduced pressure
  17. customthe residue was triturated with isopropyl ether

Sources & evidence

ORD record
ord-77be0aedd78f4f93b28a8b8cb5fb336f
Source dataset
uspto-grants-2003_02
Patent number
US06518268B1

Reaction notes

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