Hydroquinone → HCID 9794667, compound

HRID 613741Notes

Reaction equation

HRID 613741 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.[CH:12]([O:14][CH2:15][CH2:16][CH2:17][CH3:18])=[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>[CH2:15]([O:14][C: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])[CH2:16][CH2:17][CH3:18]

Participants

8

Reactant 5

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

Product 1

HCID 9794667HCID 9794667, compoundYield 21.7%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Procedure

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 ether and water. The ether phase was separated, washed with water and brine, dried, and concentrated. The residue was chromatographed on silica gel (6:1 benzene-ethyl acetate) to afford 0.254 g of the title product as a colorless oil that rapidly crystallized, mp 55°-58° C. (recrystallization solvent=hexane). 1H nmr (deuteriochloroform): δ=8.48 (m, 1 H); 8.42 (br s, 1 H); 8.24 (m, 1 H); 7.93 (m, 1 H); 4.60 (d, 1 H); 4.23 (d, 1 H); 3.84 (t, 3 H); 2.21 (s, 3 H); 177 (m, 2 H); 1.48 (m, 2 H); 0.97 (t, 3 H). ms (El): m/z=234 (M+).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for about 18 hours
  3. temperatureThe reaction mixture was then cooled
  4. concentrationconcentrated
  5. customThe ether phase was separated
  6. washwashed with water and brine
  7. customdried
  8. concentrationconcentrated
  9. customThe residue was chromatographed on silica gel (6:1 benzene-ethyl acetate)

Sources & evidence

ORD record
ord-4cb5998bd4ee4f029cef5e338069e1d4
Source dataset
uspto-grants-1999_12
Patent number
US06008361

Reaction notes

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