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

HRID 42425Notes

Reaction equation

HRID 42425 reaction equation
P(Cl)(Cl)(Cl)(Cl)Cl.O=P(Cl)(Cl)[Cl:9].O[C:13]1[CH:18]=[C:17]([CH3:19])[NH:16][C:15](=[O:20])[C:14]=1[C:21]#[N:22].[NH4+].[OH-]>C(Cl)(Cl)Cl>[Cl:9][C:13]1[CH:18]=[C:17]([CH3:19])[NH:16][C:15](=[O:20])[C:14]=1[C:21]#[N:22]

Participants

6

Reactant 4

HCID 14923Ammonium HydroxideHCID 24813Phosphorus oxychlorideHCID 24819Phosphorus pentachlorideHCID 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, PCl5 (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-aad4ffdd7e4f49deaf086b844d53cb15
Source dataset
uspto-grants-2013_09
Patent number
US08536179B2

Reaction notes

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