Hydrochloric Acid → HCID 18314014, compound

HRID 277008Notes

Reaction equation

HRID 277008 reaction equation
[H-].[Na+].[C:3](OCC)(=[O:5])[CH3:4].[C:9]([C:12]1[C:13]([CH3:24])=[C:14]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[S:15][C:16]=1[S:17][CH3:18])(=[O:11])[CH3:10].Cl>O1CCCC1.C1OCCOC2C(=CC=CC=2)OCCOCCOC2C(=CC=CC=2)OC1.C(O)C>[CH3:24][C:13]1[C:12]([C:9](=[O:11])[CH2:10][C:3](=[O:5])[CH3:4])=[C:16]([S:17][CH3:18])[S:15][C:14]=1[C:19]([O:21][CH2:22][CH3:23])=[O:20]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 8857Ethyl AcetateHCID 24758Sodium hydrideHCID 722105ETHYL 4-ACETYL-3-METHYL-5-(METHYLTHIO)THIOPHENE-2-CARBOXYLATE

Product 1

HCID 18314014HCID 18314014, compoundYield 82.6%

Reagents, catalysts & solvents 3

HCID 26541Dibenzo-18-crown-6CatalystHCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

To a suspension containing 60% sodium hydride (0.64 g, 15.9 mmol) and ethyl acetate (8.16 g, 92.9 mmol) in tetrahydrofuran (5 ml) were added in turn at room temperature a solution containing ethyl 4-acetyl-3-methyl-5-(methylthio)thiophene-2-carboxylate (2.0 g, 7.7 mmol) and ethanol (0.5 ml) in tetrahydrofuran (10 ml) and a solution containing dibenzo-18-crown-6 ether (0.04 mg) in tetrahydrofuran (5 ml), and the mixture was heated under reflux for 2 hours. The reaction solution was allowed to cool down to room temperature, made acidic by addition of 3N hydrochloric acid and extracted with ethyl acetate. The organic layer was washed (with water and saturated aqueous sodium chloride, in turn), dried (over anhydrous magnesium sulfate) and concentrated under reduced pressure. The residue thus obtained was purified by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=20:1) to afford ethyl 3-methyl-5-methylthio-4-(3-oxobutyryl)thiophene-2-carboxylate (1.91 g, 82%) as yellow -crystals.

Workup

  1. additionwere added in turn at room temperature a solution
  2. temperaturethe mixture was heated
  3. temperatureunder reflux for 2 hours
  4. extractionextracted with ethyl acetate
  5. washThe organic layer was washed (with water and saturated aqueous sodium chloride, in turn)
  6. dry with materialdried (over anhydrous magnesium sulfate)
  7. concentrationconcentrated under reduced pressure
  8. customThe residue thus obtained
  9. customwas purified by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=20:1)

Sources & evidence

ORD record
ord-cb6204ce92e745d5b5301edd67a2b977
Source dataset
uspto-grants-2002_03
Patent number
US06355663B1

Reaction notes

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