Hydrochloric Acid → 6-Methyl-2-oxo-4-propyl-1,2-dihydropyridine-3-carbonitrile

HRID 85529Notes

Reaction equation

HRID 85529 reaction equation
CC([O-])(C)C.[K+].[C:7]([CH2:9][C:10]([NH2:12])=[O:11])#[N:8].[CH3:13][C:14](=O)/[CH:15]=[CH:16]/[CH2:17][CH2:18][CH3:19].O=O.Cl>CS(C)=O.O>[CH3:13][C:14]1[NH:12][C:10](=[O:11])[C:9]([C:7]#[N:8])=[C:16]([CH2:17][CH2:18][CH3:19])[CH:15]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 977OxygenHCID 7898CyanoacetamideHCID 53645783-Hepten-2-oneHCID 23665647Potassium tert-butoxide2×

Product 1

HCID 156418016-Methyl-2-oxo-4-propyl-1,2-dihydropyridine-3-carbonitrile

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent

Procedure

To a stirred solution of t-BuOK (20 g, 178.5 mmol) and cyanoacetamide (16.5 g, 196 mmol) in DMSO (300 mL) was added (3E)-3-hepten-2-one (20 g, 178.3 mmol) under argon atmosphere at room temperature. The reaction mixture was stirred at room temperature for 30 min and then additional t-BuOK (60 g, 535.7 mmol) was added to the reaction mixture. The argon was then displaced by oxygen gas and stirred for 48 hrs at room temperature under oxygen. Reaction mixture was cooled to 0° C. and diluted with water (80 mL) followed by 4N HCl (120 mL). The mixture was stirred for 15 min and the solid was filtered. The solid was washed with water (1 L) and dried to afford 1,2-dihydro-6-methyl-2-oxo-4-propylpyridine-3-carbonitrile as an off white solid (12 g, 38%). 1H NMR (CDCl3, 400 MHz): δ 1.030 (t, 3H, J=7.2 Hz), 1.728 (m, 2H), 2.429 (s, 3H), 2.701 (t, 2H, J=7.6 Hz), 6.083 (s, 1H). LCMS E-S (M−H)=175.11.

Workup

  1. stirringstirred for 48 hrs at room temperature under oxygen
  2. customReaction mixture
  3. temperaturewas cooled to 0° C.
  4. stirringThe mixture was stirred for 15 min
  5. filtrationthe solid was filtered
  6. washThe solid was washed with water (1 L)
  7. customdried

Sources & evidence

ORD record
ord-c8beb4ed0de643da8c214ddd84a06453
Source dataset
uspto-grants-2014_09
Patent number
US08846935B2

Reaction notes

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