Hydroquinone → N-(5-acetylpyridin-2-yl)acetamide

HRID 613739Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 613739
Br[C:2]1[CH:3]=[CH:4][C:5]([NH:8][C:9](=[O:11])[CH3:10])=[N:6][CH:7]=1.[CH:12]([O:14]CCCC)=[CH2:13].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(CC)CC)C.C1(C=CC(O)=CC=1)O>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:12]([C:2]1[CH:3]=[CH:4][C:5]([NH:8][C:9](=[O:11])[CH3:10])=[N:6][CH:7]=1)(=[O:14])[CH3:13]

Komponenten

8

Edukt 5

HCID 785HydroquinoneHCID 8108Butyl vinyl etherHCID 8471TriethylamineHCID 80271Tri-o-tolylphosphineHCID 2930972-Acetamido-5-bromopyridine

Produkt 1

HCID 10797405N-(5-acetylpyridin-2-yl)acetamide

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

A mixture of 1.07 g (5 mmol) of N-(5-bromo-pyridin-2-yl)-acetamide, 1.00 g (10 mmol) of butyl vinyl ether, 0.245 g (0.8 mmol) of tri-o-tolylphosphine, 0.090 g (0.4 mmol) of palladium acetate, and 1.10 mL (7.9 mmol) of triethylamine in 10 mL of acetonitrile containing 15 mg of hydroquinone was heated at reflux for about 18 hours. The reaction mixture was then cooled, concentrated, and the residue was taken up in 10 mL of 6 M hydrochloric acid and stirred for about 15 minutes. The mixture was then diluted with 40 mL of ethyl acetate, adjusted to pH 8 with 6 M sodium hydroxide, and the aqueous phase was saturated with sodium chloride. The ethyl acetate layer was separated, dried, and concentrated. The residue was chromatographed on silica gel (2:1 ethyl acetate-hexanes), to afford 0.578 g of N-(5-acetyl-pyridin-2-yl)-acetamide as white needles, mp 146-147° C. (recrystallization solvent=1:4 ethanol-hexanes); 1H nmr (deuteriochloroform): δ=8.82 (br s, 1 H), 8.21 (m, 3 H), 2.56 (s, 3 H), 2.22 (s, 3 H); ms (NH3Cl): m/z=179 (MH+).

Aufarbeitung

  1. temperaturewas heated
  2. temperatureat reflux for about 18 hours
  3. temperatureThe reaction mixture was then cooled
  4. concentrationconcentrated
  5. additionThe mixture was then diluted with 40 mL of ethyl acetate
  6. customThe ethyl acetate layer was separated
  7. customdried
  8. concentrationconcentrated
  9. customThe residue was chromatographed on silica gel (2:1 ethyl acetate-hexanes)
  10. customto afford
  11. custom0.578 g of N-(5-acetyl-pyridin-2-yl)-acetamide as white needles, mp 146-147° C. (recrystallization solvent=1:4 ethanol-hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-6135c64a20d94ae6b0de1e1ba8bd3c92
Quelldatensatz
uspto-grants-1999_12
Patentnummer
US06008361

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