Methyl Acrylate → methyl (E)-3-(2-methoxy-5-pyrimidinyl)acrylate

HRID 474545Notes

Reaction equation

HRID 474545 reaction equation
Br[C:2]1[CH:3]=[N:4][C:5]([O:8][CH3:9])=[N:6][CH:7]=1.[C:10]([O:14][CH3:15])(=[O:13])[CH:11]=[CH2:12].C(N(CC)CC)C>CN(C=O)C.O.C(Cl)Cl.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>[CH3:9][O:8][C:5]1[N:4]=[CH:3][C:2](/[CH:12]=[CH:11]/[C:10]([O:14][CH3:15])=[O:13])=[CH:7][N:6]=1

Participants

9

Reactant 3

HCID 7294Methyl AcrylateHCID 8471TriethylamineHCID 139657Pyrimidine, 5-bromo-2-methoxy-

Product 1

HCID 10774171methyl (E)-3-(2-methoxy-5-pyrimidinyl)acrylateYield 93.6%

Reagents, catalysts & solvents 5

HCID 80271Tri-o-tolylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
130 °C

Procedure

A mixture of 5-bromo-2-(methyloxy)pyrimidine (25.0 g, 132 mmol), methyl 2-propen-oate (13.7 g, 159 mmol), palladium(II) acetate (0.297 g, 1.32 mmol), tri-o-tolylphosphine (0.805 g, 2.65 mmol) and triethylamine (29.4 g, 291 mmol) in DMF (75 mL) was heated at 130° C. under N2 for 3 h, then diluted with water (200 mL) and DCM (200 mL). The organic layer was collected, washed with water (200 mL×4) and brine, dried over sodium sulphate and concentrated to give the title compound as a pale yellow solid (24 g, 81%), which was used without further purification

Workup

  1. customThe organic layer was collected
  2. washwashed with water (200 mL×4) and brine
  3. dry with materialdried over sodium sulphate
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-a4171fd66735415b9541d25d4747676b
Source dataset
uspto-grants-2014_01
Patent number
US08637536B2

Reaction notes

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