p-Chlorothiophenol → 5-[(4-Chlorophenyl)sulfanyl]-2-thiophenecarbaldehyde

HRID 412006Notes

Reaction equation

HRID 412006 reaction equation
[H-].[Na+].[Cl:3][C:4]1[CH:9]=[CH:8][C:7]([SH:10])=[CH:6][CH:5]=1.Br[C:12]1[S:16][C:15]([CH:17]=[O:18])=[CH:14][CH:13]=1>C1COCC1>[Cl:3][C:4]1[CH:9]=[CH:8][C:7]([S:10][C:12]2[S:16][C:15]([CH:17]=[O:18])=[CH:14][CH:13]=2)=[CH:6][CH:5]=1

Participants

5

Reactant 3

HCID 7815p-ChlorothiophenolHCID 24758Sodium hydrideHCID 784285-Bromothiophene-2-carbaldehyde

Product 1

HCID 70621945-[(4-Chlorophenyl)sulfanyl]-2-thiophenecarbaldehydeYield 98%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Sodium hydride (60%, 1.2 g, 30 mmol) is added to a solution of 4-chlorothiophenol (4.3 g, 30 mmol) in THF (30 mL). The resulting solution is stirred for 10 minutes then the solvent is removed in vacuo. Acetone (60 mL) is added followed by 5-bromothiophene-2-carboxaldehyde (3.0 mL, 25 mmol). The mixture is stirred at rt for 2 h. The solvent is removed in vacuo and the resulting slurry diluted with CH2Cl2. This solution is washed three times with 1N NaOH then dried over MgSO4, filtered and concentrated in vacuo. The crude product is purified by flash column chromatography (gradient of 1 to 5% EtOAc in heptane) to give 6.2 g (98%) of 5-(4-chlorophenylsulfanyl)thiophene-2-carboxaldehyde. 1H NMR (300 MHz, CDCl3)δ7.13, 7.31-7.39, 7.63, 9.78.

Workup

  1. customthe solvent is removed in vacuo
  2. additionAcetone (60 mL) is added
  3. stirringThe mixture is stirred at rt for 2 h
  4. customThe solvent is removed in vacuo
  5. additionthe resulting slurry diluted with CH2Cl2
  6. washThis solution is washed three times with 1N NaOH
  7. dry with materialthen dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe crude product is purified by flash column chromatography (gradient of 1 to 5% EtOAc in heptane)

Sources & evidence

ORD record
ord-c8e3415c03384d3da3ab672ea673b7a9
Source dataset
uspto-grants-2003_05
Patent number
US06562816B2

Reaction notes

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