Ethylene → 2,2-Dimethyl-N-(5-vinylpyridin-2-yl)-propionamide

HRID 1596496Notes

Reaction equation

HRID 1596496 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([NH:8][C:9](=[O:14])[C:10]([CH3:13])([CH3:12])[CH3:11])=[N:6][CH:7]=1.[C:15]1(C)C=CC=C[C:16]=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C=C>C(#N)C.C(N(CC)CC)C.C(OCC)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH:15]([C:2]1[CH:3]=[CH:4][C:5]([NH:8][C:9](=[O:14])[C:10]([CH3:13])([CH3:12])[CH3:11])=[N:6][CH:7]=1)=[CH2:16]

Participants

8

Reactant 3

HCID 6325EthyleneHCID 80271Tri-o-tolylphosphineHCID 15461537N-(5-bromopyridin-2-yl)-2,2-dimethylpropanamide

Product 1

HCID 217020792,2-Dimethyl-N-(5-vinylpyridin-2-yl)-propionamideYield 738.1%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolventHCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
85 °C

Procedure

A solution of N-(5-bromopyridin-2-yl)-2,2-dimethylpropionamide (5.60 g, 21.8 mmol) in acetonitrile (20 ml) and triethylamine (5.49 ml) was treated with palladium acetate (177 mg, 0.8 mmol) and tri-o-tolylphosphine (795 g, 2.6 mmol). The mixture was placed in a pressure reactor under 130 psig of ethylene pressure and heated at 85° C. for 18 hours. The reaction mixture was cooled, vented, diluted with ethyl acetate and filtered. The ethyl acetate solution was washed sequentially with dilute citric acid, water and brine and then dried over sodium sulfate. The dried solution was filtered and evaporated. Chromatography of the residue on silica gel, eluting with dichloromethane/ethyl acetate (24:1) afforded 3.92 g (88%) of the title product as an oil. 1H NMR (CDCl3): δ=8.21 (m, 2 H); 8.03 (br, 1 H); 7.76 (d of d, 1 H); 6.63 (d of d, 1 H); 5.71 (d, 1 H); 5.25 (d, 1 H); 1.29 (s, 9H). MS (Cl): m/z=205 (M+H+).

Workup

  1. temperatureThe reaction mixture was cooled
  2. filtrationfiltered
  3. washThe ethyl acetate solution was washed sequentially with dilute citric acid, water and brine
  4. dry with materialdried over sodium sulfate
  5. filtrationThe dried solution was filtered
  6. customevaporated
  7. washChromatography of the residue on silica gel, eluting with dichloromethane/ethyl acetate (24:1)

Sources & evidence

ORD record
ord-5f22c7c93cc14a26a8ac7093a0c9c3b1
Source dataset
uspto-grants-2001_09
Patent number
US06291489B1

Reaction notes

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