Sodium Hydroxide → 5-Chloro-3-nitropyridine-2-carboxylic acid

HRID 1897988Notes

Reaction equation

HRID 1897988 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([N+:14]([O-:16])=[O:15])[C:5]([C:8]#CC(C)(O)C)=[N:6][CH:7]=1.[O-:17][Mn](=O)(=O)=O.[K+].[OH-:23].[Na+]>O>[Cl:1][C:2]1[CH:3]=[C:4]([N+:14]([O-:16])=[O:15])[C:5]([C:8]([OH:17])=[O:23])=[N:6][CH:7]=1

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 516875Potassium PermanganateHCID 579425324-(5-Chloro-3-nitro-pyridin-2-yl)-2-methyl-but-3-yn-2-ol

Product 1

HCID 534081275-Chloro-3-nitropyridine-2-carboxylic acid

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
77.5 °C

Procedure

A suspension of the alkyne from step 1 (1.96 g, 8.2 mmol) in water (20 mL) was heated at 75-80° C. KMnO4 (4.27 g, 27.1 mmol) was added portion wise over 30 min. After complete addition, heating was continued for 45 min. The reaction mixture was then cooled to room temperature and the pH adjusted to 9 by the addition of 1.0 M aqueous NaOH and filtered through filter paper. The filter cake was thoroughly washed with 0.3 M aqueous NaOH. The filtrate was extracted with EtOAc and discarded. The aqueous part was acidified to pH 3-4 with 1 M HCl and saturated with solid NaCl. This solution was extracted with EtOAc (4×30 mL). The combined extract was dried (Na2SO4) and concentrated under reduced pressure to provide the crude acid (500 mg). MS m/z: 200.8 (M−H).

Workup

  1. additionAfter complete addition
  2. temperatureheating
  3. temperatureThe reaction mixture was then cooled to room temperature
  4. filtrationfiltered
  5. filtrationthrough filter paper
  6. washThe filter cake was thoroughly washed with 0.3 M aqueous NaOH
  7. extractionThe filtrate was extracted with EtOAc
  8. extractionThis solution was extracted with EtOAc (4×30 mL)
  9. extractionThe combined extract
  10. dry with materialwas dried (Na2SO4)
  11. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-393376e7898b4423a25222c3e935657c
Source dataset
uspto-grants-2013_08
Patent number
US08519135B2

Reaction notes

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