Iodine → Methyl 6-amino-5-iodopyridine-3-carboxylate

HRID 1515576Notes

Reaction equation

HRID 1515576 reaction equation
[NH2:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][N:3]=1.[I:12]I>CO.[Ag+].FC(F)(F)C([O-])=O>[CH3:9][O:8][C:6](=[O:7])[C:5]1[CH:10]=[C:11]([I:12])[C:2]([NH2:1])=[N:3][CH:4]=1

Participants

5

Reactant 2

HCID 807IodineHCID 737487Methyl 6-aminonicotinate

Product 1

HCID 15350913Methyl 6-amino-5-iodopyridine-3-carboxylateYield 77%

Reagents, catalysts & solvents 2

HCID 76299Silver trifluoroacetateCatalystHCID 887MethanolSolvent

Conditions

Temperature
25 °C

Procedure

To a stirred suspension of methyl 6-aminonicotinate (10 g, 65.7 mmol) and trifluoroacetic acid silver salt (36.3 g, 164.3 mmol) in methanol (250 mL) was added iodine (41.7 g, 164.3 mmol) at 25° C. and the reaction mixture was stirred at 25° C. for 72 h. The mixture was filtered, washed with methanol and concentrated in vacuo. The residue was dissolved in ethyl acetate and washed consecutively with a saturated sodium thiosulfate solution, brine and dried over anhydrous sodium sulfate. The solvent was evaporated in vacuo to afford 6-amino-5-iodo-nicotinic acid methyl ester (13.8 g, 77%) as a light yellow solid: 1H NMR (400 MHz, CDCl3) δ ppm 3.89 (s, 3H), 5.46 (br. s., 2H), 8.47 (br. s., 1H), 8.67 (br. s., 1H).

Workup

  1. filtrationThe mixture was filtered
  2. washwashed with methanol
  3. concentrationconcentrated in vacuo
  4. dissolutionThe residue was dissolved in ethyl acetate
  5. washwashed consecutively with a saturated sodium thiosulfate solution, brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. customThe solvent was evaporated in vacuo

Sources & evidence

ORD record
ord-6f9c03877083405c8592a27604ad83c8
Source dataset
uspto-grants-2012_07
Patent number
US08222416B2

Reaction notes

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