Acetaldehyde → HCID 21548596, compound

HRID 1605106Notes

Reaction equation

HRID 1605106 reaction equation
[C:1]1([NH:7]N)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH:9](=[O:11])C.[C:12]1(NN)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(=[O:22])C.[S:23]1[CH:27]=[CH:26][CH:25]=[C:24]1[C:28](Cl)=[O:29]>O.N1C=CC=CC=1.C1C=CC=CC=1.CCOCC>[C:24]1([C:28]([N:7]2[C:15]3[CH2:16][CH2:17][CH:12]([C:9]([OH:11])=[O:22])[CH2:13][C:14]=3[C:6]3[C:1]2=[CH:2][CH:3]=[CH:4][CH:5]=3)=[O:29])[S:23][CH:27]=[CH:26][CH:25]=1

Participants

9

Reactant 4

HCID 177AcetaldehydeHCID 7516PhenylhydrazineHCID 789282-Thiophenecarbonyl chlorideHCID 21510619HCID 21510619, compound

Product 1

HCID 21548596HCID 21548596, compound

Reagents, catalysts & solvents 4

HCID 241BenzeneSolventHCID 962WaterSolventHCID 1049PyridineSolventHCID 3283Diethyl EtherSolvent

Procedure

To 22 ml. of phenylhydrazine in 22 ml. of ether was added 22 ml. of acetaldehyde, gentle reflux being maintained with external cooling, and the solution was allowed to stand for one-half hour. Benzene was added and the solution was dried over magnesium sulfate, filtered, dried over calcium sulfate, and evaporated to dryness under reduced pressure below 35°C. The residue was dissolved in pentane and the mixture was chilled and filtered to give 6.9 g. of acetaldehyde phenylhydrazine, a cold solution of which in 20 ml. pyridine was treated dropwise with 7.33 g. of 2-thienylcarbonyl chloride. The solution was warmed to room temperature, diluted with water and extracted with ether. The ether extract was washed with water, dilute acetic acid, water, sodium carbonate solution and water, dried and evaporated to dryness. The acetaldehyde 1-(2-thenoyl)-1-phenylhydrazone was dissolved in absolute ethyl alcohol, 15 ml. of a 4-N solution of hydrogen chloride in absolute ethyl alcohol was added, and the solution was diluted with ether, chilled and filtered and the filtrate was evaporated to dryness under reduced pressure. A solution of the crude 1-(2-thenoyl)-1-phenylhydrazine hydrochloride in acetic acid containing 5 ml. of acetic acid saturated with hydrogen chloride was added to 3.1 g. of cyclohexanone-4-carboxylic acid and the mixture was warmed on a steam bath for about two hours, cooled to room temperature, diluted with 10 ml. of water and chilled. The resulting precipitate was collected, washed with 75% acetic acid in water and dried to yield 4.7 g. of the title compound; m.p. 180°-182°C.

Workup

  1. temperaturebeing maintained with external cooling
  2. waitto stand for one-half hour
  3. dry with materialthe solution was dried over magnesium sulfate
  4. filtrationfiltered
  5. dry with materialdried over calcium sulfate
  6. customevaporated to dryness under reduced pressure below 35°C
  7. dissolutionThe residue was dissolved in pentane
  8. temperaturethe mixture was chilled
  9. filtrationfiltered
  10. customto give 6.9 g
  11. extractionextracted with ether
  12. extractionThe ether extract
  13. washwas washed with water, dilute acetic acid, water, sodium carbonate solution and water
  14. customdried
  15. customevaporated to dryness
  16. dissolutionThe acetaldehyde 1-(2-thenoyl)-1-phenylhydrazone was dissolved in absolute ethyl alcohol
  17. additionof a 4-N solution of hydrogen chloride in absolute ethyl alcohol was added
  18. additionthe solution was diluted with ether
  19. temperaturechilled
  20. filtrationfiltered
  21. customthe filtrate was evaporated to dryness under reduced pressure
  22. additionof acetic acid saturated with hydrogen chloride was added to 3.1 g
  23. temperatureof cyclohexanone-4-carboxylic acid and the mixture was warmed on a steam bath for about two hours
  24. temperaturecooled to room temperature
  25. additiondiluted with 10 ml
  26. temperatureof water and chilled
  27. customThe resulting precipitate was collected
  28. washwashed with 75% acetic acid in water
  29. customdried
  30. customto yield 4.7 g

Sources & evidence

ORD record
ord-5fdcd9258e9f448ea43205569094b5b6
Source dataset
uspto-grants-1976_04
Patent number
US03948939

Reaction notes

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