Lithium hydroxide, monohydrate → HCID 86675418, compound

HRID 407262Notes

Reaction equation

HRID 407262 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]C)=[O:12])[C:3]=1[O:15][CH3:16].O.[OH-].[Li+]>C1COCC1.CO.O>[NH2:1][C:2]1[C:7]([F:8])=[C:6]([CH:9]=[CH2:10])[N:5]=[C:4]([C:11]([OH:13])=[O:12])[C:3]=1[O:15][CH3:16]

Participants

6

Reactant 2

HCID 168937Lithium hydroxide, monohydrateHCID 86675408Methyl 4-amino-5-fluoro-3-methoxy-6-vinylpicolinate

Product 1

HCID 86675418HCID 86675418, compoundYield 60.2%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of methyl 4-amino-5-fluoro-3-methoxy-6-vinylpicolinate (140.0 mg, 0.619 mmol) in THF (1.2 mL), MeOH (1.200 mL), Water (0.600 mL), lithium hydroxide hydrate (78 mg, 1.857 mmol) was charged as a solid. The reaction was allowed to stir at room temperature for 18 hrs. The reaction was concentrated to dryness. The resulting residue was diluted with 2 N HCl and MeOH. The product was purified (C18 10-80% ACN in H2O 12 CV) to yield 4-amino-5-fluoro-3-methoxy-6-vinylpicolinic acid (79 mg, 0.372 mmol, 60.2% yield). ESIMS for m/z 213 (M+H)+. 1H NMR (400 MHz, DMSO-d6) δ 3.73 (s, 3H), 5.50 (dd, J=11.0, 2.2 Hz, 1H), 6.20 (dd, J=17.3, 2.2 Hz, 1H), 6.35 (s, 2H), 6.83 (ddd, J=17.3, 10.9, 1.7 Hz, 1H), 12.98 (s, 1H). 19F NMR (376 MHz, DMSO-d6) δ −145.09.

Workup

  1. concentrationThe reaction was concentrated to dryness
  2. additionThe resulting residue was diluted with 2 N HCl and MeOH
  3. customThe product was purified (C18 10-80% ACN in H2O 12 CV)

Sources & evidence

ORD record
ord-f2b804ff7b43430a8e6d95979f2b28e6
Source dataset
uspto-grants-2014_06
Patent number
US08754229B2

Reaction notes

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