Dimethylamine → 1-(3-Pyridyl)-3-(dimethylamino)-2-propen-1-one

HRID 440866Notes

Reaction equation

HRID 440866 reaction equation
[Na].[CH3:2]O.[C:4]([C:7]1[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=1)(=[O:6])[CH3:5].C(OCC)=O.[CH3:18][NH:19][CH3:20]>C1(C)C=CC=CC=1.C(O)(=O)C>[CH3:18][N:19]([CH3:2])[CH:20]=[CH:5][C:4]([C:7]1[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=1)=[O:6]

Participants

8

Reactant 5

HCID 674DimethylamineHCID 887MethanolHCID 8025Ethyl formateHCID 95893-AcetylpyridineHCID 5360545Sodium

Product 1

HCID 5670331-(3-Pyridyl)-3-(dimethylamino)-2-propen-1-one

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 1140TolueneSolvent4×

Procedure

8 g (0.35 mol) of sodium are placed in 260 ml of toluene and at 100° made into a suspension using a vibromixer. After cooling to 0°, 17 ml (0.42 mol) of methanol are added dropwise, with cooling, and the mixture is then stirred for 45 minutes at 75°. At 25° and with ice-cooling, a solution of 38.5 ml (0.35 mol) of 3-acetylpyridine and 28 ml (0.35 mol) of ethyl formate in 300 ml of toluene are added dropwise in the course of 45 minutes. The yellow suspension is stirred for 16 hours at 25° and then 23.7 g (0.52 mol) of dimethylamine are added. After the addition of 100 ml of toluene, the mixture is stirred for 45 minutes at 25°, and then at 0° a solution of 20 ml of acetic acid in 150 ml of toluene is added dropwise in the course of 30 minutes and the mixture is then boiled at reflux for 1 hour. After cooling to 25°, the mixture is filtered and washed with 500 ml of toluene/hexane (1:1) and the filtrate is concentrated until crystallisation begins. Cooling to 0°, filtration and drying at 80° under HV yield 3-dimethylamino-1-(3-pyridyl)-2-propen-1one; m.p. 81°-82°.

Workup

  1. temperatureAfter cooling to 0°
  2. temperaturewith cooling
  3. temperatureAt 25° and with ice-cooling
  4. stirringThe yellow suspension is stirred for 16 hours at 25°
  5. stirringthe mixture is stirred for 45 minutes at 25°
  6. temperatureat reflux for 1 hour
  7. temperatureAfter cooling to 25°
  8. filtrationthe mixture is filtered
  9. washwashed with 500 ml of toluene/hexane (1:1)
  10. concentrationthe filtrate is concentrated until crystallisation
  11. temperatureCooling to 0°
  12. filtrationfiltration
  13. customdrying at 80° under HV

Sources & evidence

ORD record
ord-ec8b82e21452435793def2f79726e613
Source dataset
uspto-grants-1996_05
Patent number
US05521184

Reaction notes

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