Methyl iodide → Methyl 2-chloronicotinate

HRID 487061Notes

Reaction equation

HRID 487061 reaction equation
[Cl:1][C:2]1[N:10]=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[H-].[Na+].[H][H].[CH3:15]I>CN(C)C=O>[Cl:1][C:2]1[N:10]=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([O:6][CH3:15])=[O:5]

Participants

6

Reactant 4

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 762582-Chloronicotinic acidHCID 178418361HCID 178418361, compound

Product 1

HCID 819931Methyl 2-chloronicotinate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

15.75 g (0.1 mole) of commercially available 2-chloronicotinic acid was dissolved in 100 mL of N,N-dimethylformamide. After cooling this solution to 0° under nitrogen, 4.4 g (0.11 mole) of 60% sodium hydride was added portionwise while evolved hydrogen gas was vented. The reaction mixture was stirred until the effervescence stopped (~2 hrs.). 7.5 mL (0.112 mole) of methyl iodide was then added dropwise. Stirring of the reaction mixture was continued overnight. Solvent was removed in vacuo at r.t. The resulting brown residue was partitioned between ethyl acetate and water. The organic phase was then washed with brine and dried over anhydrous magnesium sulfate. Solvent removal gave a residue which was purified on silica gel using 1:1 ethyl acetate:hexane mixture to give the desired methyl 2-chloronicotinate as oil.

Workup

  1. temperatureAfter cooling this solution to 0° under nitrogen
  2. custom(~2 hrs.)
  3. stirringStirring of the reaction mixture
  4. customSolvent was removed in vacuo at r.t
  5. customThe resulting brown residue was partitioned between ethyl acetate and water
  6. washThe organic phase was then washed with brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customSolvent removal
  9. customgave a residue which
  10. customwas purified on silica gel using 1:1 ethyl acetate

Sources & evidence

ORD record
ord-3e06b14caaf644b8b47b1aae909a1c16
Source dataset
uspto-grants-1994_03
Patent number
US05294610

Reaction notes

Loading…