Ethylene → N-(5-Ethenylpyridin-2-yl)acetamide

HRID 431267Notes

Reaction equation

HRID 431267 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([NH:8][C:9](=[O:11])[CH3:10])=[N:6][CH:7]=1.[C:12]1(C)C=CC=C[C:13]=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C=C>C(#N)C.C(N(CC)CC)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH:12]([C:2]1[CH:3]=[CH:4][C:5]([NH:8][C:9](=[O:11])[CH3:10])=[N:6][CH:7]=1)=[CH2:13]

Participants

7

Reactant 3

HCID 6325EthyleneHCID 80271Tri-o-tolylphosphineHCID 2930972-Acetamido-5-bromopyridine

Product 1

HCID 15477709N-(5-Ethenylpyridin-2-yl)acetamideYield 1,924.4%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
85 °C

Procedure

A solution of of N-(5-bromo-pyridin-2-yl)-acetamide (prepared as described in Preparation One, 4.30 g, 20 mmol) in acetonitrile (15 ml) and triethylamine (5.04 ml) was treated with palladium acetate (45 mg, 0.2 mmol) and tri-o-tolylphosphine (203 mg, 0.66 mmol). The mixture was placed in a pressure reactor under 50 psig of ethylene pressure and heated at 85° C. for 66 hours. The reaction mixture was cooled, vented, and partitioned between phosphate buffer (0.1M, pH 6.6) and ethyl acetate. The aqueous phase was extracted with ethyl acetate twice more. The combined ethyl acetate extracts were washed with additional phosphate buffer, brine and dried over sodium sulfate. The extracts were filtered and evaporated to afford 2.06 g (63%) of the title product as a flaky crystalline residue. Recrystallization from ethyl acetate/cyclohexane gave colorless flakes. mp 120-121° C. 1H NMR (CDCl3): δ=8.55 (br, 1H); 8.24 (d, 1H); 8.15 (d, 1H); 7.76 (d of d, 1H); 6.64 (d of d, 1H); 5.73 (d, 1H); 5.28 (d, 1H); 2.19 (s, 3H). MS (CI): m/z=163 (M+H+).

Workup

  1. temperatureThe reaction mixture was cooled
  2. custompartitioned between phosphate buffer (0.1M, pH 6.6) and ethyl acetate
  3. extractionThe aqueous phase was extracted with ethyl acetate twice more
  4. washThe combined ethyl acetate extracts were washed with additional phosphate buffer, brine
  5. dry with materialdried over sodium sulfate
  6. filtrationThe extracts were filtered
  7. customevaporated

Sources & evidence

ORD record
ord-3058fbc5f06c442d8667552157229491
Source dataset
uspto-grants-2003_12
Patent number
US06657063B1

Reaction notes

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