Acetic Acid → 5-(Ethylthio)picolinic acid

HRID 331551Notes

Reaction equation

HRID 331551 reaction equation
[CH2:1]([S-:3])[CH3:2].[Na+].[N+]([C:8]1[CH:9]=[CH:10][C:11]([C:14]([O:16]C)=[O:15])=[N:12][CH:13]=1)([O-])=O.C(O)(=O)C>CN(C=O)C>[CH2:1]([S:3][C:8]1[CH:9]=[CH:10][C:11]([C:14]([OH:16])=[O:15])=[N:12][CH:13]=1)[CH3:2]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 4459711Sodium ethanethiolateHCID 12457882Methyl 5-nitropicolinate

Product 1

HCID 670196615-(Ethylthio)picolinic acidYield 79%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Sodium ethanethiolate (1.6 g, 17.2 mmol) was added to a solution of methyl 5-nitropicolinate (2.8 g, 16 mmol) in DMF (30 mL), and the resulting mixture was stirred a room temperature. After 3 hours, acetic acid (1 mL) was added, and the mixture was evaporated to dryness. The residue was suspended in methanol (50 mL) and treated with 3N NaOH. The resulting mixture was stirred at room temperature for 16 hours and then evaporated. The residue was dissolved in water (100 mL), washed with ethyl acetate (2×100 mL), and acidified to pH 3-4 (conc. HCl), resulting in precipitation of the product. The precipitate was filtered, rinsed with water (100 mL) and dried under vacuum, providing 2.3 g of 5-(ethylthio)picolinic acid, in 79% yield; 1H NMR (DMSO-d6) δ 1.23 (t, 3H, J=7.3 Hz), 3.14 (q, 2H, J=7.3 Hz), 7.86 (dd, 1H, J=8.4 Hz, J=2.4 Hz), 7.95 (dd, 1H, J=8.4 Hz, J=0.9 Hz), 8.57 (dd, 1H, J=2.4 Hz, J=0.9 Hz), 13.09 (br, 1H).

Workup

  1. customthe mixture was evaporated to dryness
  2. additiontreated with 3N NaOH
  3. stirringThe resulting mixture was stirred at room temperature for 16 hours
  4. customevaporated
  5. dissolutionThe residue was dissolved in water (100 mL)
  6. washwashed with ethyl acetate (2×100 mL)
  7. customresulting in precipitation of the product
  8. filtrationThe precipitate was filtered
  9. washrinsed with water (100 mL)
  10. customdried under vacuum

Sources & evidence

ORD record
ord-1b36ee62761f4967ba9cca51a8ea8279
Source dataset
uspto-grants-2014_11
Patent number
US08877780B2

Reaction notes

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