Formaldehyde → 5-Acetyl-2,6-dimethyl-1,4-dihydro-pyridine-3-carbonitrile

HRID 2390412Notes

Reaction equation

HRID 2390412 reaction equation
[CH3:1]/[C:2](/[NH2:6])=[CH:3]\[C:4]#[N:5].[CH3:7][C:8](=O)[CH2:9][C:10](=[O:12])[CH3:11].[CH2:14]=O>N1CCCCC1.C(O)C>[C:10]([C:9]1[CH2:14][C:3]([C:4]#[N:5])=[C:2]([CH3:1])[NH:6][C:8]=1[CH3:7])(=[O:12])[CH3:11]

Participants

6

Reactant 3

HCID 712FormaldehydeHCID 31261AcetylacetoneHCID 53247203-Aminocrotonitrile

Product 1

HCID 671047185-Acetyl-2,6-dimethyl-1,4-dihydro-pyridine-3-carbonitrileYield 59.1%

Reagents, catalysts & solvents 2

HCID 8082PiperidineCatalystHCID 702EthanolSolvent

Procedure

A mixture of 3-aminocrotonitrile (2.0 g, 24 mmol), 2,4-pentanedione (4.9 g, 49 mmol), paraformaldehyde (1.5 g, 49 mmol) and piperidine (12 drops) in ethanol (100 mL) was heated to reflux for 4 hours, cooled and concentrated to dryness. The residue was treated with diethyl ether (150 mL). The solid was collected and washed with ether. The solid was triturated with dichloromethane (2×100 mL). The combined dichloromethane triturations were concentrated to provide 2.5 g of the title compound. 1H NMR (DMSO-d6) δ ppm 1.92 (t, J=1.02 Hz, 3 H), 2.09 (s, 3 H), 2.10 (s, 3 H), 3.20 (s, 2 H), 8.65 (s, 1 H). MS (DCI-NH3) [M+H]+ at 177.

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 4 hours
  3. temperaturecooled
  4. concentrationconcentrated to dryness
  5. additionThe residue was treated with diethyl ether (150 mL)
  6. customThe solid was collected
  7. washwashed with ether
  8. customThe solid was triturated with dichloromethane (2×100 mL)
  9. concentrationThe combined dichloromethane triturations were concentrated

Sources & evidence

ORD record
ord-5f5891e5bcea47458ecc29fa490e5c64
Source dataset
uspto-grants-2012_09
Patent number
US08273767B2

Reaction notes

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