Methyl Acrylate → methyl (2E)-3-(pyrimidin-5-yl)prop-2-enoate

HRID 474542Notes

Reaction equation

HRID 474542 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[N:6][CH:7]=1.[C:8]([O:12][CH3:13])(=[O:11])[CH:9]=[CH2:10]>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>[N:4]1[CH:3]=[C:2](/[CH:10]=[CH:9]/[C:8]([O:12][CH3:13])=[O:11])[CH:7]=[N:6][CH:5]=1

Participants

6

Reactant 2

HCID 7294Methyl AcrylateHCID 783445-Bromopyrimidine

Product 1

HCID 18470237methyl (2E)-3-(pyrimidin-5-yl)prop-2-enoateYield 66.4%

Reagents, catalysts & solvents 3

HCID 80271Tri-o-tolylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Procedure

A solution of 5-bromopyrimidine (22.82 g, 144 mmol), methyl 2-propenoate (14.83 g, 172 mmol), palladium(II) acetate (0.322 g, 1.435 mmol), tri-o-tolylphosphine (0.874 g, 2.87 mmol), and TEA (32.0 g, 316 mmol) in DMF (100 mL) was heated at 130° C. under N2 for 7 h. After cooling, the reaction mixture was partitioned between water (200 mL) and DCM (200 mL). The organic phase was collected, washed with water (200 mL×4), brine, dried over sodium sulphate, and concentrated in vacuo to give the crude title compound as a pale yellow solid (18.4 g, 95 mmol, 66.4%). LCMS: rt=1.01 min, [M+H+]=165

Workup

  1. temperatureAfter cooling
  2. customthe reaction mixture was partitioned between water (200 mL) and DCM (200 mL)
  3. customThe organic phase was collected
  4. washwashed with water (200 mL×4), brine
  5. dry with materialdried over sodium sulphate
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-f5f7dcef2127411a9c0a9d80b76d682d
Source dataset
uspto-grants-2014_01
Patent number
US08637536B2

Reaction notes

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