Hydrochloric Acid → 5-cyano-6-ethoxy-3-nitropicolinic Acid

HRID 2407838Notes

Reaction equation

HRID 2407838 reaction equation
[CH2:1]([O:3][C:4]1[N:11]=[C:10]([CH:12]=[O:13])[C:9]([N+:14]([O-:16])=[O:15])=[CH:8][C:5]=1[C:6]#[N:7])[CH3:2].CC(=CC)C.Cl([O-])=[O:23].[Na+].O.P([O-])(O)(O)=O.[Na+].Cl>O1CCOCC1.O1CCCC1.O.C(OCC)(=O)C>[C:6]([C:5]1[CH:8]=[C:9]([N+:14]([O-:16])=[O:15])[C:10]([C:12]([OH:23])=[O:13])=[N:11][C:4]=1[O:3][CH2:1][CH3:2])#[N:7]

Participants

10

Reactant 5

HCID 313Hydrochloric AcidHCID 105532-Methyl-2-buteneHCID 516949Sodium Phosphate, Monobasic, MonohydrateHCID 23668197Sodium ChloriteHCID 585040872-Ethoxy-6-formyl-5-nitronicotinonitrile

Product 1

HCID 585043075-cyano-6-ethoxy-3-nitropicolinic AcidYield 24.5%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

To a stirred solution of the compound prepared in Example 446 (0.61 g) in dioxane (10 mL) at ambient temperature was added of a 2 mol/L solution of 2-methyl-2-butene in tetrahydrofuran (8.4 mL). To the resulting stirred solution was added a solution of sodium chlorite (80%, 1.37 g) and sodium dihydrogen phosphate monohydrate (1.37 g) in water (8 mL). The resulting mixture was vigorously stirred at ambient temperature for 18 hours. The reaction mixture was diluted with ethyl acetate (15 mL), and after stirring for 10 minutes, the mixture was transferred to a separatory funnel. The aqueous layer was acidified with 6M hydrochloric acid to pH 1.5, and then extracted with chloroform (20 mL). The organic layer was dried over sodium sulfate and concentrated to provide the title compound (0.16 g) with the following physical data.

Workup

  1. stirringThe resulting mixture was vigorously stirred at ambient temperature for 18 hours
  2. stirringafter stirring for 10 minutes
  3. customthe mixture was transferred to a separatory funnel
  4. extractionextracted with chloroform (20 mL)
  5. dry with materialThe organic layer was dried over sodium sulfate
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-a278d5b7dcb240068e356be7393ca259
Source dataset
uspto-grants-2014_08
Patent number
US08809538B2

Reaction notes

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