Dimethylformamide → 2-(4-Chlorophenyl)-3-(dimethylamino)acrylaldehyde

HRID 1733563Notes

Reaction equation

HRID 1733563 reaction equation
P(Cl)(Cl)(Cl)=O.[CH3:6][N:7]([CH3:10])[CH:8]=O.[Cl:11][C:12]1[CH:17]=[CH:16][C:15]([CH2:18][C:19](O)=[O:20])=[CH:14][CH:13]=1.C(=O)([O-])[O-].[K+].[K+]>C1(C)C=CC=CC=1>[Cl:11][C:12]1[CH:17]=[CH:16][C:15]([C:18](=[CH:8][N:7]([CH3:10])[CH3:6])[CH:19]=[O:20])=[CH:14][CH:13]=1

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 15880(4-Chlorophenyl)acetic acidHCID 24813Phosphorus oxychloride

Product 1

HCID 34489722-(4-Chlorophenyl)-3-(dimethylamino)acrylaldehyde

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a slurry of Vilsmeyer reagent, (formed from a stirred mixture of 92.0 g. of phosphorus oxychloride and 73.0 g. of N,N-dimethylformamide at a temperature below 10° C.) is added 34.12 g. of 4-chlorophenylacetic acid. This mixture is stirred at ambient temperature for 30 minutes, then is heated to 70°-80° C. during which time the mixture becomes effervescent. The mixture is kept at 70°-80° C. for 5.5 hours, then is allowed to cool. The cooled mixture is slowly poured onto cracked ice, and ice is added intermittently to maintain the temperature of the mixture below 15° C. during the portionwise addition of potassium carbonate and until pH 10 is achieved. Then 150 ml. of toluene is added and the mixture is heated on a steam bath for one hour. After cooling, the layers are separated and the aqueous layer is extracted with an additional 100 ml. of toluene. The organic layers are combined, copiously washed with water, dried over anhydrous sodium sulfate and evaporated at reduced pressure to yield a yellow solid. The solid is recrystallized from hexane to give 27.3 g. of the product of the Example as a tan solid, mp. 121°-124° C.

Workup

  1. customTo a slurry of Vilsmeyer reagent, (formed from a stirred mixture of 92.0 g
  2. temperatureis heated to 70°-80° C. during which time the mixture
  3. waitThe mixture is kept at 70°-80° C. for 5.5 hours
  4. temperatureto cool
  5. additionThe cooled mixture is slowly poured
  6. additionis added intermittently
  7. temperatureto maintain the temperature of the mixture below 15° C.
  8. temperaturethe mixture is heated on a steam bath for one hour
  9. temperatureAfter cooling
  10. customthe layers are separated
  11. extractionthe aqueous layer is extracted with an additional 100 ml
  12. washcopiously washed with water
  13. dry with materialdried over anhydrous sodium sulfate
  14. customevaporated at reduced pressure
  15. customto yield a yellow solid
  16. customThe solid is recrystallized from hexane
  17. customto give 27.3 g

Sources & evidence

ORD record
ord-d5a17698b5114d618a74fdb3b1f4dc61
Source dataset
uspto-grants-1980_12
Patent number
US04242515

Reaction notes

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