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

HRID 378560

反応式

HRID 378560 の反応式
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]

参加物

8

反応物 5

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 6342Acetonitrile溶媒

実験手順

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+).

後処理

  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)

出典と根拠

ORDレコード
ord-0ea8551e0cf74be6a04995f2f6848111
出典データセット
uspto-grants-2000_02
特許番号
US06031105

関連ノート

読み込み中…