Water → HCID 67209520, compound

HRID 402504Notes

Reaction equation

HRID 402504 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:10](Br)=[CH:9][C:8]([CH3:12])=[CH:7][N:6]=1)=[O:4].[CH3:13][O:14][C:15](=[O:18])[CH:16]=[CH2:17].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.O>CCOC(C)=O.[CH2-]C=C.[CH2-]C=C.Cl[Pd+].Cl[Pd+].C1(C)C=CC=CC=1.CC(N(C)C)=O>[CH3:1][O:2][C:3]([C:5]1[C:10]([CH:17]=[CH:16][C:15]([O:14][CH3:13])=[O:18])=[CH:9][C:8]([CH3:12])=[CH:7][N:6]=1)=[O:4]

Participants

9

Reactant 4

HCID 962WaterHCID 7294Methyl AcrylateHCID 80271Tri-o-tolylphosphineHCID 49853419Methyl 3-bromo-5-methylpyridine-2-carboxylate

Product 1

HCID 67209520HCID 67209520, compoundYield 80.2%

Reagents, catalysts & solvents 4

HCID 61538Palladium, di-mu-chlorobis(eta3-2-propenyl)di-CatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolventHCID 31374DimethylacetamideSolvent

Conditions

Temperature
115 °C

Procedure

3-Bromo-5-methyl-pyridine-2-carboxylic acid methyl ester (1.6 g, 6.945 mmol), methylacrylate (1.50 g, 17.39 mmol), allylpalladium(II) chloride dimer (0.127 g, 0.348 mmol), tri-o-tolylphosphine (0.212 g, 0.695 mmol), water free sodium carbonate (2.211 g, 20.9 mmol), and N,N.dimethylacetamide (4.56 ml) were added to toluene (15 ml) and the reaction mixture was stirred for 18 h at 115° C. in a microwave apparatus. The mixture was diluted with EtOAc, washed with brine, dried over sodium sulfate, and the solvents were evaporated under reduced pressure. The residue was purified by chromatography on silica (Flashmaster, hex to hex/EtOAc 2/3 over 40 min, 20 min hex/EtOAc 2/3) to give the product as off-white solid (1.31 g, 80%). [1H-NMR (DMSO-d6, 600 MHz) δ 8.51 (s, 1H), 8.20 (s, 1H), 8.10 (d, 1H), 6.69 (d, 1H), 3.88 (s, 3H), 3.74 (s, 3H), 2.39 (s, 3H); LCMS RtL=2.753 min; [M+H]+=236.0]

Workup

  1. washwashed with brine
  2. dry with materialdried over sodium sulfate
  3. customthe solvents were evaporated under reduced pressure
  4. customThe residue was purified by chromatography on silica (Flashmaster, hex to hex/EtOAc 2/3 over 40 min, 20 min hex/EtOAc 2/3)

Sources & evidence

ORD record
ord-007a9b25d17d49a6bda8556608bdb0ce
Source dataset
uspto-grants-2014_06
Patent number
US08742106B2

Reaction notes

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