Ethylene → HCID 20687262, compound

HRID 1596497Notes

Reaction equation

HRID 1596497 reaction equation
[CH3:1][O:2][C:3](=[O:12])[NH:4][C:5]1[CH:10]=[CH:9][C:8](Br)=[CH:7][N:6]=1.[C:13]1(C)C=CC=C[C:14]=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>[CH3:1][O:2][C:3](=[O:12])[NH:4][C:5]1[CH:10]=[CH:9][C:8]([CH:13]=[CH2:14])=[CH:7][N:6]=1

Participants

8

Reactant 3

HCID 6325EthyleneHCID 80271Tri-o-tolylphosphineHCID 790797Methyl (5-bromopyridin-2-yl)carbamate

Product 1

HCID 20687262HCID 20687262, compoundYield 439.1%

Reagents, catalysts & solvents 4

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

Conditions

Temperature
85 °C

Procedure

A solution of (5-bromo-pyridin-2-yl)-carbamic acid methyl ester (1.68 g, 7.2 mmol) in acetonitrile (15 ml) and triethylamine (1.84 ml) was treated with palladium acetate (65 mg, 0.29 mmol) and tri-o-tolylphosphine (295 mg, 0.97 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 and diluted with ethyl acetate and filtered. The ethyl acetate solution was washed sequentially with 1M aqueous citric acid, water, brine and was dried over sodium sulfate and filtered. The filtrate was evaporated. The residue was recrystallized from dichloromethane-hexane to afford 0.759 g (58%) of the title product as colorless crystals. mp 146-148° C. 1H NMR (CDCl3): δ=9.04 (br, 1 H); 8.28 (d, 1 H); 7.97 (d, 1 H); 7.77 (d of d, 1 H); 6.64 (d of d, 1 H); 5.71 (d, 1 H); 5.26 (d, 1 H); 3.81 (s, 3H). MS (Cl): m/z=179 (M+H+).

Workup

  1. temperatureThe reaction mixture was cooled
  2. filtrationfiltered
  3. washThe ethyl acetate solution was washed sequentially with 1M aqueous citric acid, water, brine
  4. dry with materialwas dried over sodium sulfate
  5. filtrationfiltered
  6. customThe filtrate was evaporated
  7. customThe residue was recrystallized from dichloromethane-hexane

Sources & evidence

ORD record
ord-2e74719f805d4c0d8b538c6337b0e0b9
Source dataset
uspto-grants-2001_09
Patent number
US06291489B1

Reaction notes

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