Methyl 2,4-dichloropyrimidine-6-carboxylate → Methyl 2-chloropyrimidine-4-carboxylate

HRID 2264419Notes

Reaction equation

HRID 2264419 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:10]=[C:9](Cl)[N:8]=[C:7]([Cl:12])[N:6]=1)=[O:4].[H][H]>C(O)C.[Pd]>[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][N:8]=[C:7]([Cl:12])[N:6]=1)=[O:4]

Participants

5

Reactant 2

HCID 239689Methyl 2,4-dichloropyrimidine-6-carboxylateHCID 178418361HCID 178418361, compound

Product 1

HCID 43811076Methyl 2-chloropyrimidine-4-carboxylate

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

To a solution of 2,6-dichloro-pyrimidine-4-carboxylic acid methyl ester (2.0 g, 9.66 mmol, 1.0 equiv; commercially available from Peakdale Molecular, UK) in ethanol (50 mL) was added palladium on activated charcoal 5% (0.10 g, 0.048 mmol, 0.5 equiv) and the reaction vessel filled with hydrogen (2.5 bar). After stirring at rt for 18 h, the reaction mixture was filtered over celite, concentrated under reduced pressure and the residue purified by silica column chromatography using a MPLC system (CombiFlash Companion, Isco Inc.) eluting with a gradient of heptane/ethyl acetate providing 0.19 g (11%) of the title compound. 1H NMR (300 MHz, CDCl3): δ 3.97 (s, 3H), 7.89 (d, J=4.9 Hz, 1H), 8.81 (d, J=4.9 Hz, 1H). 13C NMR (75 MHz, CDCl3): δ 52.67, 118.22, 156.45, 160.62, 161.18, 162.31. MS (ISP): 172.5 [M+H]+.

Workup

  1. filtrationthe reaction mixture was filtered over celite
  2. concentrationconcentrated under reduced pressure
  3. customthe residue purified by silica column chromatography
  4. washeluting with a gradient of heptane/ethyl acetate providing 0.19 g (11%) of the title compound

Sources & evidence

ORD record
ord-dc94ce06cf294375b5220ee359e24d32
Source dataset
uspto-grants-2010_12
Patent number
US07855194B2

Reaction notes

Loading…