Ethyl propiolate → 6-Hydroxy-2-methylnicotinonitrile

HRID 574114Notes

Reaction equation

HRID 574114 reaction equation
[CH3:1]/[C:2](/[NH2:6])=[CH:3]\[C:4]#[N:5].[C:7](OCC)(=[O:10])[C:8]#[CH:9]>CN(C=O)C>[CH3:1][C:2]1[NH:6][C:7](=[O:10])[CH:8]=[CH:9][C:3]=1[C:4]#[N:5]

Participants

4

Reactant 2

HCID 12182Ethyl propiolateHCID 53247203-Aminocrotonitrile

Product 1

HCID 113785166-Hydroxy-2-methylnicotinonitrileYield 31.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

(Synthesis 1991, 894-896.) 3-Aminocrotonitrile (29, 2.9 g, 36 mmol) and ethyl propiolate (30, 3.0 mL, 36 mmol) were dissolved in dry DMF (17 mL). The reaction mixture was stirred for 1 h at room temperature, and the mixture was heated at reflux for 3 d. The precipitate formed after cooling to room temperature was collected, washed with methanol (5 mL), ether (10 mL), and dried to yield 131 (1.5 g, 31%): mp>300° C. 1H NMR (300 MHz, DMSO-d6) δ 12.43 (s, 1H), 7.58 (d, J=9.6 Hz, 1H), 6.23 (d, J=9.6 Hz, 1H), 2.37 (s, 3H).

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux for 3 d
  3. customThe precipitate formed
  4. temperatureafter cooling to room temperature
  5. customwas collected
  6. washwashed with methanol (5 mL), ether (10 mL)
  7. customdried

Sources & evidence

ORD record
ord-5528727b12ac4edda59fe13bd1c2b827
Source dataset
uspto-grants-2015_05
Patent number
US09034870B2

Reaction notes

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