Ammonium Hydroxide → 4-CHLORO-6-METHYL-2-OXO-1,2-DIHYDROPYRIDINE-3-CARBONITRILE

HRID 62324Notes

Reaction equation

HRID 62324 reaction equation
O=P(Cl)(Cl)[Cl:3].O[C:7]1[CH:12]=[C:11]([CH3:13])[NH:10][C:9](=[O:14])[C:8]=1[C:15]#[N:16].[NH4+].[OH-]>C(Cl)(Cl)Cl>[Cl:3][C:7]1[CH:12]=[C:11]([CH3:13])[NH:10][C:9](=[O:14])[C:8]=1[C:15]#[N:16]

Participants

5

Reactant 3

HCID 14923Ammonium HydroxideHCID 24813Phosphorus oxychlorideHCID 547209421,2-Dihydro-4-hydroxy-6-methyl-2-oxo-3-pyridinecarbonitrile

Product 1

HCID 113896344-CHLORO-6-METHYL-2-OXO-1,2-DIHYDROPYRIDINE-3-CARBONITRILEYield 40%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

Using a 100 ml round bottom with reflux condenser, PCI5 (6.7 g, 32 mmol), POCl3 (3.0 mL, 32 mmol) and 30 ml CHCl3 (dry) were stirred for 5 min (see: Heterocycles, vol. 60, No. 6, 2003, 1461-1468). Added 4-hydroxy-6-methyl-2-oxo-1,2-dihydro-3-pyridinecarbonitrile (4 g, 26.6 mmol) and stirred for 2 h at 80° C. Quenched reaction while hot and poured into 1 L beaker with 100 “g” ice, 24 mL NH4OH, pH by paper was 8-9. Stirred 5 min and filtered. Washed solid with water. Suspended solid in ethanol and filtered and washed with ethanol. Gave: 4-chloro-6-methyl-2-oxo-1,2-dihydro-3-pyridinecarbonitrile (1.7 g, 9.58 mmol, 40% yield)1H NMR (400 MHz, DMSO-d6) δ ppm 12.85 (br. s., 1H) 6.53 (s, 1H) 2.28 (s, 3H) MS(ES) [M+H]+ 168.9.

Workup

  1. temperaturewith reflux condenser
  2. customQuenched
  3. customreaction while hot and
  4. additionpoured into 1 L beaker with 100 “
  5. filtrationfiltered
  6. washWashed solid with water
  7. filtrationfiltered
  8. washwashed with ethanol
  9. customGave

Sources & evidence

ORD record
ord-6f68149b3b8b4a38b5c72cbe5f092b3d
Source dataset
uspto-grants-2016_09
Patent number
US09446041B2

Reaction notes

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