Ethanol → 4-Phenyl-4-sulfanylidenebutan-2-one

HRID 1731548Notes

Reaction equation

HRID 1731548 reaction equation
C[O-].[Na+].[C:4](O)(=[S:6])[CH3:5].BrCC([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=O.[CH2:18]([OH:20])[CH3:19]>CCOCC>[C:18]([CH2:5][C:4]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[S:6])(=[O:20])[CH3:19]

Participants

6

Reactant 4

HCID 702Ethanol2×HCID 6259Phenacyl bromideHCID 10942334Sodium MethoxideHCID 178418634HCID 178418634, compound

Product 1

HCID 233560534-Phenyl-4-sulfanylidenebutan-2-one

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a solution of 54.0 g (1.0M) sodium methoxide in 100 ml absolute ethanol stirring under nitrogen at reflux temperature 74 ml (76.1 g, 1.0M) thioacetic acid is added dropwise over a period of 0.5 hours. Upon complete addition the solution is refluxed for 15 minutes. To the yellow solution stirring under nitrogen atmosphere at reflux temperature, a solution of 199.1 g (1.0M) α-bromoacetophenone in 800 ml absolute ethanol is added rapidly dropwise over a period of 70 minutes. After complete addition, the suspension formed is refluxed for 3 hours. The reaction mixture is cooled and the precipitated NaBr is removed by vacuum filtration. The filtrate is concentrated in vacuo to give a brown oil with some solid present. This mixture is suspended in 500 ml of ether and is filtered to remove insoluble NaBr. The filtrate is stirred with activated charcoal for 0.5 hours, filtered, and concentrated in vacuo to give a red-brown oil. This oil is purified by vacuum distillation and the fraction is collected at 133°-137°/0.2-0.05 mm Hg and characterized by NMR as α-acetylthioacetophenone.

Workup

  1. additionis added dropwise over a period of 0.5 hours
  2. additionUpon complete addition the solution
  3. temperatureis refluxed for 15 minutes
  4. temperatureat reflux temperature
  5. additionAfter complete addition
  6. customthe suspension formed
  7. temperatureis refluxed for 3 hours
  8. temperatureThe reaction mixture is cooled
  9. customthe precipitated NaBr is removed by vacuum filtration
  10. concentrationThe filtrate is concentrated in vacuo
  11. customto give a brown oil with some solid present
  12. filtrationis filtered
  13. customto remove insoluble NaBr
  14. stirringThe filtrate is stirred with activated charcoal for 0.5 hours
  15. filtrationfiltered
  16. concentrationconcentrated in vacuo
  17. customto give a red-brown oil
  18. distillationThis oil is purified by vacuum distillation
  19. customthe fraction is collected at 133°-137°/0.2-0.05 mm Hg

Sources & evidence

ORD record
ord-19df323271604851b54e0eb740658708
Source dataset
uspto-grants-1986_11
Patent number
US04622322

Reaction notes

Loading…