2,6-Dichloro-4-methylnicotinamide → 2,6-Dichloro-4-methylpyridine-3-carboxylic acid

HRID 1063518Notes

Reaction equation

HRID 1063518 reaction equation
N([O-])=[O:2].[Na+].[Cl:5][C:6]1[N:14]=[C:13]([Cl:15])[CH:12]=[C:11]([CH3:16])[C:7]=1[C:8](N)=[O:9]>O.S(=O)(=O)(O)O>[Cl:5][C:6]1[N:14]=[C:13]([Cl:15])[CH:12]=[C:11]([CH3:16])[C:7]=1[C:8]([OH:2])=[O:9]

Participants

5

Reactant 2

HCID 3348552,6-Dichloro-4-methylnicotinamideHCID 23668193Sodium Nitrite

Product 1

HCID 6761212,6-Dichloro-4-methylpyridine-3-carboxylic acidYield 97%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 1118Sulfuric AcidSolvent

Procedure

A solution of sodium nitrite (2.73 g, 39.6 mmol) in water (15 mL) was added slowly to a solution of commercially available (Maybridge) 2,6-dichloro-4-methyl-nicotinamide (4.5 g, 22 mmol) in concentrated sulfuric acid resulting in evolution of heat and brown gas. The mixture was stirred at room temperature for 15 min, and then heated to 60° C. for 7 h. The solution was cooled to 0° C. and then water (15 mL) was added. The resulting white precipitate was collected by filtration and washed with hexane. The aqueous filtrate was extracted with EtOAc (3×) and the combined organic extracts were dried over MgSO4 and concentrated in vacuo. The residue was combined with the white precipitate to afford 2,6-dichloro-4-methyl-nicotinic acid (4.39 g, 97%) as a white solid: LCMS RT: 1.20 min, MH+: 206.3.

Workup

  1. temperatureof heat
  2. temperatureheated to 60° C. for 7 h
  3. temperatureThe solution was cooled to 0° C.
  4. filtrationThe resulting white precipitate was collected by filtration
  5. washwashed with hexane
  6. extractionThe aqueous filtrate was extracted with EtOAc (3×)
  7. dry with materialthe combined organic extracts were dried over MgSO4
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-e6f5510e2b14478a93a7148020039d9f
Source dataset
uspto-grants-2005_11
Patent number
US06964971B2

Reaction notes

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