Triethylamine → tert-Butyl (2E)-3-(3-aminopyridin-2-yl)acrylate

HRID 217653Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 217653
[NH2:1][C:2]1[C:3](Br)=[N:4][CH:5]=[CH:6][CH:7]=1.[C:9]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])(=[O:12])[CH:10]=[CH2:11].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(CC)CC)C>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[NH2:1][C:2]1[C:3](/[CH:11]=[CH:10]/[C:9]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])=[N:4][CH:5]=[CH:6][CH:7]=1

Komponenten

7

Edukt 4

HCID 8471TriethylamineHCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 6428163-Amino-2-bromopyridine

Produkt 1

HCID 59168063tert-Butyl (2E)-3-(3-aminopyridin-2-yl)acrylate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

950 mg (4.94 mmol) of the bromide from Example 5A, 1900 mg (14.83 mmol) of tert-butyl acrylate, 330 mg (1.50 mmol) of palladium(II) acetate, 450 mg (1.50 mmol) of tri-ortho-tolylphospine are dissolved in 15 ml of acetonitrile, and 1000 mg (9.88 mmol) of triethylamine are added. The mixture is stirred under reflux for 16 h. The reaction mixture is concentrated, mixed with ethyl acetate and washed with saturated aqueous sodium chloride solution. The organic phase is dried over sodium sulphate, filtered, concentrated and purified by column chromatography on silica gel with cyclohexane/ethyl acetate (7:3). 95 mg (6% of theory) of product are obtained.

Aufarbeitung

  1. temperatureunder reflux for 16 h
  2. concentrationThe reaction mixture is concentrated
  3. additionmixed with ethyl acetate
  4. washwashed with saturated aqueous sodium chloride solution
  5. dry with materialThe organic phase is dried over sodium sulphate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. custompurified by column chromatography on silica gel with cyclohexane/ethyl acetate (7:3)
  9. custom95 mg (6% of theory) of product are obtained

Quellen und Nachweise

ORD-Eintrag
ord-cb63c1bf778e49f4bcd0b8a50b47bb81
Quelldatensatz
uspto-grants-2012_06
Patentnummer
US08198282B2

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