Malonic Acid → HCID 54106316, compound

HRID 2166693Notes

Reaction equation

HRID 2166693 reaction equation
[CH3:1][N:2]([CH2:4][C:5]1[S:9][C:8]([CH:10]=O)=[CH:7][CH:6]=1)[CH3:3].N1CCCCC1.C(O)(=O)[CH2:19][C:20]([OH:22])=[O:21]>N1C=CC=CC=1>[CH3:3][N:2]([CH2:4][C:5]1[S:9][C:8]([CH:10]=[CH:19][C:20]([OH:22])=[O:21])=[CH:7][CH:6]=1)[CH3:1]

Participants

5

Reactant 3

HCID 867Malonic AcidHCID 8082PiperidineHCID 200989295-[(dimethylamino)methyl]thiophene-2-carbaldehyde

Product 1

HCID 54106316HCID 54106316, compoundYield 54.8%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

5-(Dimethylaminomethyl)thiophene-2-carboxaldehyde (40.09 g) and piperidine (3 ml) were added to a solution of malonic acid (24.65 g) in pyridine (150 ml). The mixture was stirred under reflux for 7 hours. During the reaction a solid precipitated and slowly re-dissolved. The solution was allowed to cool and was then poured on to 2 M hydrochloric acid (150 ml). The volume of the solution was reduced to about 120 ml by evaporation at reduced pressure and extracted with diethyl ether. The ether extracts were washed with water. The aqueous phase was cooled and the solid, which precipitated out, was filtered off and washed with water-isopropanol. More solid was obtained by evaporating the filtrate to about 100 ml and adding isopropanol and cooling the mixture in ice for about 15 minutes. This solid was filtered off, and washed with isopropanol. The solids were combined and recrystallised from isopropanol-water to give 3-(5-dimethylaminomethyl-2-thienyl)acrylic acid (27.45 g) m.p. 223.5°-225° C.

Workup

  1. temperatureunder reflux for 7 hours
  2. customDuring the reaction a solid
  3. customprecipitated
  4. dissolutionslowly re-dissolved
  5. temperatureto cool
  6. additionwas then poured on to 2 M hydrochloric acid (150 ml)
  7. customThe volume of the solution was reduced to about 120 ml by evaporation at reduced pressure
  8. extractionextracted with diethyl ether
  9. washThe ether extracts were washed with water
  10. temperatureThe aqueous phase was cooled
  11. customthe solid, which precipitated out
  12. filtrationwas filtered off
  13. washwashed with water-isopropanol
  14. customMore solid was obtained
  15. customby evaporating the filtrate to about 100 ml
  16. additionadding isopropanol
  17. temperaturecooling the mixture in ice for about 15 minutes
  18. filtrationThis solid was filtered off
  19. washwashed with isopropanol
  20. customrecrystallised from isopropanol-water

Sources & evidence

ORD record
ord-8202c50037c94171a6a7d48b3b1e4899
Source dataset
uspto-grants-1983_06
Patent number
US04388317

Reaction notes

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