Dimethylformamide → 3-Chloro-3-(4-fluorophenyl)-2-(4-methylthiophenyl)acrylaldehyde

HRID 1090870Notes

Reaction equation

HRID 1090870 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=O)[CH2:9][C:10]2[CH:15]=[CH:14][C:13]([S:16][CH3:17])=[CH:12][CH:11]=2)=[CH:4][CH:3]=1.CN(C)[CH:21]=[O:22].P(Cl)(Cl)([Cl:26])=O>C(Cl)(Cl)Cl>[Cl:26][C:8]([C:5]1[CH:6]=[CH:7][C:2]([F:1])=[CH:3][CH:4]=1)=[C:9]([C:10]1[CH:15]=[CH:14][C:13]([S:16][CH3:17])=[CH:12][CH:11]=1)[CH:21]=[O:22]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 24813Phosphorus oxychlorideHCID 112539741-(4-Fluorophenyl)-2-(4-methylthiophenyl)ethanone

Product 1

HCID 538776633-Chloro-3-(4-fluorophenyl)-2-(4-methylthiophenyl)acrylaldehydeYield 96%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

A 48 g quantity (0.18 mole) of 1-(4-fluorophenyl)-2-(4-methylthiophenyl)-ethanone was suspended in a mixture of 500 ml of chloroform and 57 ml (0.74 mole) of N,N-dimethylformamide. To the suspension was added dropwise 60 ml (0.64 mole) of phosphorus oxychloride with stirring over a period of 30 minutes with cooling in an ice-saline solution bath. After the addition, the resulting mixture was further stirred at 20° C. for 2 hours and refluxed with heating for 18 hours. After being cooled to room temperature, the reaction mixture was added to ice water and then extracted with chloroform. The organic layer was washed with water and a saturated saline solution in this sequence and dried over magnesium sulfate, followed by concentration under reduced pressure. The resulting crystals were washed with a 1:3 mixture of diethyl ether and n-hexane, giving 53 g (94%) of the desired product in the form of a mixture of E- and Z-isomers as light brown solids.

Workup

  1. temperaturewith cooling in an ice-saline solution bath
  2. additionAfter the addition
  3. stirringthe resulting mixture was further stirred at 20° C. for 2 hours
  4. temperaturerefluxed
  5. temperaturewith heating for 18 hours
  6. extractionextracted with chloroform
  7. washThe organic layer was washed with water
  8. dry with materiala saturated saline solution in this sequence and dried over magnesium sulfate
  9. concentrationfollowed by concentration under reduced pressure
  10. washThe resulting crystals were washed with a 1:3 mixture of diethyl ether and n-hexane

Sources & evidence

ORD record
ord-e1361d36df47430fa7156f81e7532cbd
Source dataset
uspto-grants-1992_01
Patent number
US05082974

Reaction notes

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