Propyne → (3-Prop-1-ynylpyridin-4-yl)carbamic acid tert-butyl ester

HRID 400608Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 400608
[CH:1]#[C:2][CH3:3].[C:4]([O:8][C:9](=[O:18])[NH:10][C:11]1[CH:16]=[CH:15][N:14]=[CH:13][C:12]=1I)([CH3:7])([CH3:6])[CH3:5].C(OCC)(=O)C.[Cl-].[NH4+]>CN(C=O)C.C(N(CC)CC)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[C:4]([O:8][C:9](=[O:18])[NH:10][C:11]1[CH:16]=[CH:15][N:14]=[CH:13][C:12]=1[C:1]#[C:2][CH3:3])([CH3:7])([CH3:6])[CH3:5]

Komponenten

9

Edukt 4

HCID 6335PropyneHCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 10903275(3-Iodo-pyridin-4-yl)-carbamic acid tert-butyl ester

Produkt 1

HCID 11031741(3-Prop-1-ynylpyridin-4-yl)carbamic acid tert-butyl esterAusbeute 98 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 6228DimethylformamideLösungsmittelHCID 8471TriethylamineLösungsmittel

Versuchsvorschrift

Propyne (6.3 mL, 124 mmol) was condensed in a pressure tube at −78° C. A solution of (3-iodopyridin-4-yl)carbamic acid tert-butyl ester (7.98 g, 24.9 mmol) in 15 mL of DMF, 60 mL of triethylamine, dichlorobis(triphenylphosphine)palladium (II) (877 mg, 1.25 mmol), and CuI (472 mg, 2.49 mmol) were added, and the tube was sealed and stirred at room temperature overnight. 200 mL of ethyl acetate and 100 mL of saturated aqueous ammonium chloride solution were added, the phases were separated and the aqueous layer was extracted with three 100 mL portions of ethyl acetate. The combined organic layers were dried over magnesium sulfate, filtered, and concentrated in vacuo. Chromatography on SiO2 (25% to 40% ethyl acetate in hexanes, gradient) afforded 5.65 g of (3-prop-1-ynylpyridin-4-yl)carbamic acid tert-butyl ester (98% yield).

Aufarbeitung

  1. customcondensed in a pressure tube at −78° C
  2. customthe tube was sealed
  3. customthe phases were separated
  4. extractionthe aqueous layer was extracted with three 100 mL portions of ethyl acetate
  5. dry with materialThe combined organic layers were dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-1651c747b4ee4cd181fbb69cce7c9731
Quelldatensatz
uspto-grants-2014_06
Patentnummer
US08741897B2

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