Ammonia → 2-Cyanoethyl 3-aminocrotonate

HRID 2254147Notes

Reaction equation

HRID 2254147 reaction equation
C=C1OC(=O)C1.[C:7]([O:13][CH2:14][CH2:15][C:16]#[N:17])(=[O:12])[CH2:8][C:9]([CH3:11])=O.[NH3:18]>C(C#N)CO.CN(C)C1C=CN=CC=1.O1CCCC1>[NH2:18]/[C:9](/[CH3:11])=[CH:8]\[C:7]([O:13][CH2:14][CH2:15][C:16]#[N:17])=[O:12]

Participants

7

Reactant 3

HCID 222AmmoniaHCID 12661DiketeneHCID 123604062-Cyanoethyl 3-oxobutanoate

Product 1

HCID 136714102-Cyanoethyl 3-aminocrotonateYield 36%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 8011HydracrylonitrileSolventHCID 8028TetrahydrofuranSolvent

Procedure

In 37.5 g of 95% ethylene cyanohydrin was dissolved 100 mg of 4-dimethylaminopyridine, and 38.6 ml of diketene was added thereto dropwise at 70° to 80° C. for one hour under stirring, following by stirring at 70° to 80° C. for 2 hours. Sixty two grams of the resulting crude 2-cyanoethyl acetoacetate was dissolved in 400 ml of tetrahydrofuran. To the solution was added 20 g of molecular sieves 4A, following by blowing an ammonia gas for 2 hours with stirring under ice-cooling. The resulting solution was stirred in a container closed with a rubber stopper at a room temperature for 18 hours. Molecular sieves 4A was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a yellow crystal. Recrystallization from ethyl acetate/n-hexane gave 22.2 g (yield: 36%) of 2-cyanoethyl 3-aminocrotonate as a pale yellow crystal.

Workup

  1. additionwas added
  2. stirringby stirring at 70° to 80° C. for 2 hours
  3. customfor 2 hours
  4. stirringwith stirring under ice-
  5. temperaturecooling
  6. stirringThe resulting solution was stirred in a container
  7. customclosed with a rubber stopper at a room temperature for 18 hours
  8. customwas removed by filtration
  9. concentrationthe filtrate was concentrated under reduced pressure
  10. customto obtain a yellow crystal
  11. customRecrystallization from ethyl acetate/n-hexane

Sources & evidence

ORD record
ord-17c6e52b07674feba9fa4aa664a62eed
Source dataset
uspto-grants-1993_08
Patent number
US05234821

Reaction notes

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