Sodium Hydroxide → 4-Amino-2,6-diethylpyridine-3-carboxylic acid

HRID 2254892Notes

Reaction equation

HRID 2254892 reaction equation
[NH2:1][C:2]([CH2:6][CH3:7])=[CH:3][C:4]#[N:5].[C:8]([CH2:12][C:13]([O:15]C)=O)(=O)[CH2:9][CH3:10].[OH-:17].[Na+]>CO>[NH2:5][C:4]1[CH:3]=[C:2]([CH2:6][CH3:7])[N:1]=[C:8]([CH2:9][CH3:10])[C:12]=1[C:13]([OH:15])=[O:17]

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 121699Methyl 3-oxovalerateHCID 714097573-Amino-2-pentenenitrile

Product 1

HCID 200942464-Amino-2,6-diethylpyridine-3-carboxylic acid

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Methyl 4-amino-2,6-diethylpyridine-3-carboxylate (3.94 g), itself obtained using an analogous procedure to that described in Example 2B but starting from 3-amino-2-pentenenitrile (obtained a described in J. Het. Chem., 1989, 26, 1575) and methyl propionylacetate, was added to a mixture of 2M sodium hydroxide solution (9.5 ml) and methanol (40 ml) and the mixture was heated at reflux for 16 hours. The solution was cooled to ambient temperature and volatile material was removed by evaporation. The residue was partitioned between ethyl acetate and a mixture of 2M hydrochloric acid (9.5 ml) and water (20 ml). The aqueous phase was separated, water was removed by evaporation and the residue was extracted with ethyl acetate/methanol (1:1 v/v). The combined organic extracts were filtered and solvent was removed from the filtrate by evaporation to give 4-amino-2,6-diethylpyridine-3-carboxylic acid (3.46 g) as a yellow-brown foam; NMR (d6 -DMSO): 1.18(m,6H), 2.64(q,2H), 3.12(q,2H), 6.49(s,1H), 8.28(broad s,2H),; mass spectrum (chemical ionisation, ammonia): 195(M+H)+.

Workup

  1. customobtained
  2. temperaturethe mixture was heated
  3. temperatureat reflux for 16 hours
  4. customvolatile material was removed by evaporation
  5. customThe residue was partitioned between ethyl acetate
  6. additiona mixture of 2M hydrochloric acid (9.5 ml) and water (20 ml)
  7. customThe aqueous phase was separated
  8. customwater was removed by evaporation
  9. extractionthe residue was extracted with ethyl acetate/methanol (1:1 v/v)
  10. filtrationThe combined organic extracts were filtered
  11. customsolvent was removed from the filtrate by evaporation

Sources & evidence

ORD record
ord-ac8bc58bd5b34d9db9a6b8dcb4c108e0
Source dataset
uspto-grants-1993_08
Patent number
US05236937

Reaction notes

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