Bromine → Methyl 4,6-dibromo-3-hydroxypicolinate

HRID 530192Notes

Reaction equation

HRID 530192 reaction equation
[BrH:1].[NH2:2][CH:3]([C:8]1[O:9][CH:10]=[CH:11][CH:12]=1)[C:4]([O:6][CH3:7])=[O:5].C([O-])(=O)C.[Na+].[Br:18]Br>O.CO>[Br:1][C:12]1[CH:11]=[C:10]([Br:18])[N:2]=[C:3]([C:4]([O:6][CH3:7])=[O:5])[C:8]=1[OH:9]

Participants

6

Reactant 3

HCID 24408BromineHCID 517045Sodium AcetateHCID 118647338Methyl 2-amino-2-(furan-2-yl)acetate hydrobromide

Product 1

HCID 22175130Methyl 4,6-dibromo-3-hydroxypicolinateYield 51.6%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

To a magnetically stirred solution of methyl 2-amino-2-(furan-2-yl)acetate hydrobromide (0.84 g, 3.56 mmol) and sodium acetate (1.255 g, 15.30 mmol) in 40 mL of water at 0° C. was added dropwise a solution of bromine (0.788 ml, 15.30 mmol) in 10 mL of MeOH over 30 min. After warming to room temperature for 24 hr, the reaction mixture was filtered through a fritted glass funnel and the white solid was washed with water. Solvent removal gave methyl 4,6-dibromo-3-hydroxypicolinate (577 mg, 1.837 mmol, 51.6% yield) as a white solid; Mp 180-181° C. (recrystallized from heptane). 1H NMR (600 MHz, Chloroform-d) δ 11.35 (s, 1H), 7.86 (s, 1H), 4.07 (s, 3H); 13C NMR (151 MHz, Chloroform-d) δ 168.74, 156.02, 136.85, 130.14, 129.92, 124.67, 53.84. HRMS-ESI (m/z) calc'd for [C7H5Br2NO3]+, 308.8636. found, 308.8638.

Workup

  1. filtrationthe reaction mixture was filtered through a fritted glass funnel
  2. washthe white solid was washed with water
  3. customSolvent removal

Sources & evidence

ORD record
ord-77248b8987814f5397eec5cb8c7913ab
Source dataset
uspto-grants-2016_05
Patent number
US09353060B2

Reaction notes

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