Cyanoacetamide → Ethyl 5-cyano-1,6-dihydro-2-methyl-6-oxo-3-pyridinecarboxylate

HRID 622093Notes

Reaction equation

HRID 622093 reaction equation
[CH2:1]([O:3][C:4](=[O:9])[CH2:5][C:6]([CH3:8])=O)[CH3:2].C[O:11][CH:12](OC)[N:13](C)C.[C:18]([CH2:20][C:21](N)=O)#[N:19].[H-].[Na+]>C1COCC1.C(O)(=O)C>[CH2:1]([O:3][C:4]([C:5]1[CH:21]=[C:20]([C:18]#[N:19])[C:12](=[O:11])[NH:13][C:6]=1[CH3:8])=[O:9])[CH3:2]

Participants

7

Reactant 4

HCID 7898CyanoacetamideHCID 8868Ethyl AcetoacetateHCID 24758Sodium hydrideHCID 78373Dimethylformamide dimethyl acetal

Product 1

HCID 3016759Ethyl 5-cyano-1,6-dihydro-2-methyl-6-oxo-3-pyridinecarboxylateYield 45.6%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent

Procedure

Ethylacetoacetate (6.5 g, 0.050 mole) and dimethylformamide dimethyl acetal (7.14 g, 0.060 mole) were stirred together under argon overnight. The resulting reddish oil was concentrated on the rotary evaporator and the concentrate then dissolved in THF (10 ml) and quickly added to a suspension of cyanoacetamide (4.20 g, 0.050 mole) and sodium hydride in THF (175 ml). The reaction mixture was neutralized to pH 6 with acetic acid and concentrated on the rotary evaporator. The residue was triturated with a 50:50 CH2Cl2 -H2O mixture collected and recrystallized (EtOAC) giving 4.7 g of 3-cyano-1,2-dihydro-6-methyl-2-oxo-5-pyridinecarboxylic acid ethyl ester m.pt. 208°-210° C.

Workup

  1. concentrationThe resulting reddish oil was concentrated on the rotary evaporator
  2. concentrationthe concentrate
  3. dissolutionthen dissolved in THF (10 ml)
  4. concentrationconcentrated on the rotary evaporator
  5. customThe residue was triturated with a 50:50 CH2Cl2 -H2O mixture
  6. customcollected
  7. customrecrystallized (EtOAC)

Sources & evidence

ORD record
ord-8d44fcbb4734414fa5684d5727a723f0
Source dataset
uspto-grants-1988_09
Patent number
US04769380

Reaction notes

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