Methyl 4-amino-5-fluoro-6-vinylpicolinate → Methyl 4-amino-6-ethyl-5-fluoropicolinate

HRID 244321Notes

Reaction equation

HRID 244321 reaction equation
[NH2:1][C:2]1[C:7]([F:8])=[C:6]([CH:9]=[CH2:10])[N:5]=[C:4]([C:11]([O:13][CH3:14])=[O:12])[CH:3]=1>C(O)C.[Pd]>[NH2:1][C:2]1[C:7]([F:8])=[C:6]([CH2:9][CH3:10])[N:5]=[C:4]([C:11]([O:13][CH3:14])=[O:12])[CH:3]=1

Participants

4

Reactant 1

HCID 70496887Methyl 4-amino-5-fluoro-6-vinylpicolinate

Product 1

HCID 70497131Methyl 4-amino-6-ethyl-5-fluoropicolinateYield 90.2%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

Pd/C (0.976 g, 0.459 mmol) was added to a 500 mL Parr bottle and methyl 4-amino-5-fluoro-6-vinylpicolinate (0.9 g, 4.59 mmol) dissolved in ethanol (50 ml) was added. The Parr bottle was placed on a Parr shaker, purged with nitrogen gas three times, and pressurized to 43 psi with hydrogen gas. The reaction mixture was shaken on the Parr Shaker for 45 min The catalyst was removed via filtration through celite. The celite was washed with ethyl acetate. The filtrates were combined and concentrated under vacuum to provide the title compoud as a white solid (820 mg, 4.14 mmol, 90% yield); 1H NMR (400 MHz, DMSO-d6) δ 1.17 (t, J=7.6 Hz, 3H), 2.68 (qd, J=7.6, 2.7 Hz, 2H), 3.80 (s, 3H), 6.39 (s, 2H), 7.34 (d, J=6.7 Hz, 1H; 19F NMR (376 MHz, DMSO-d6) δ −147.65; ESIMS m/z 199 ([M+H]+), 197 ([M−H]−).

Workup

  1. additionwas added
  2. custompurged with nitrogen gas three times
  3. customwas removed via filtration through celite
  4. washThe celite was washed with ethyl acetate
  5. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-34a99f1233cc4e109760c5213f3b443b
Source dataset
uspto-grants-2014_02
Patent number
US08658568B2

Reaction notes

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