Ethanol → Alpha-(4-Picolylthio)acetophenone

HRID 1389793Notes

Reaction equation

HRID 1389793 reaction equation
C[O-].[Na+].C(O)C.[N:7]1[CH:12]=[CH:11][C:10]([CH2:13][SH:14])=[CH:9][CH:8]=1.Br[CH2:16][C:17]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:18]>C(OCC)C>[N:7]1[CH:12]=[CH:11][C:10]([CH2:13][S:14][CH2:16][C:17]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[O:18])=[CH:9][CH:8]=1

Participants

6

Reactant 4

HCID 702Ethanol3×HCID 6259Phenacyl bromideHCID 10942334Sodium MethoxideHCID 13092602Pyridin-4-ylmethanethiol

Product 1

HCID 13490316Alpha-(4-Picolylthio)acetophenone

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Under a nitrogen atmosphere, sodium methoxide (0.81 g., 15 mmoles) was dissoled in 17.9 ml. of stirring absolute ethanol, and cooled in an ice bath. 4-Picolyl mercaptan (1.88 g., 15 mmoles) in 3 ml. of absolute ethanol was added dropwise over approximately 5 minutes, followed by alpha-bromoacetophenone (3.05 g., 15 mmoles) in 10 ml. of warm absolute ethanol added over approximately 10 minutes. The stirring reaction mixture was warmed to room temperature and left to stir for 17 hours. Salts were removed by filtration through diatomaceous earth, and the solids repulped for 0.5 hour with additional ethanol and refiltered. The ethanol filtrates were combined and concentrated to yield a waxy solid. The waxy solid was taken up in approximately 11 volumes of diethyl ether, treated with activated carbon, filtered and the mother liquor concentrated to a solid (1.90 g.). Recrystallization from diethyl ether/hexane gave purified alpha-(4-picolylthio)acetophenone (1.25 g. in two crops, m.p. 55°-59° C., ir (KBr): 5.92, 6.18, 7.00, 7.76, 9.78, 12.38, 13.70μ).

Workup

  1. temperaturecooled in an ice bath
  2. customThe stirring reaction mixture
  3. waitleft
  4. customSalts were removed by filtration through diatomaceous earth
  5. waitthe solids repulped for 0.5 hour with additional ethanol
  6. concentrationconcentrated
  7. customto yield a waxy solid
  8. additiontreated with activated carbon
  9. filtrationfiltered
  10. concentrationthe mother liquor concentrated to a solid (1.90 g.)
  11. customRecrystallization from diethyl ether/hexane
  12. customgave
  13. custompurified alpha-(4-picolylthio)acetophenone (1.25 g. in two crops, m.p. 55°-59° C., ir (KBr): 5.92, 6.18, 7.00, 7.76, 9.78, 12.38, 13.70μ)

Sources & evidence

ORD record
ord-caecff7706174e06bbbc4caf00b03ba3
Source dataset
uspto-grants-1981_01
Patent number
US04246263

Reaction notes

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