Triethylamine → [4-(4-Cyanophenyl)but-3-ynyl]carbamic acid tert-butyl ester

HRID 81339

Reaktionsgleichung

Reaktionsgleichung von HRID 81339
[C:1]([O:5][C:6](=[O:12])[NH:7][CH2:8][CH2:9][C:10]#[CH:11])([CH3:4])([CH3:3])[CH3:2].I[C:14]1[CH:21]=[CH:20][C:17]([C:18]#[N:19])=[CH:16][CH:15]=1.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.C1COCC1>[C:1]([O:5][C:6](=[O:12])[NH:7][CH2:8][CH2:9][C:10]#[C:11][C:14]1[CH:21]=[CH:20][C:17]([C:18]#[N:19])=[CH:16][CH:15]=1)([CH3:4])([CH3:3])[CH3:2]

Komponenten

7

Edukt 3

HCID 8471TriethylamineHCID 764674-IodobenzonitrileHCID 10725815tert-Butyl 3-butyn-1-ylcarbamate

Produkt 1

HCID 67364707[4-(4-Cyanophenyl)but-3-ynyl]carbamic acid tert-butyl esterAusbeute 99 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

But-3-ynylcarbamic acid tert-butyl ester (3.66 g, 22 mmol) was added dropwise to an ice cooled, stirring, argon purged mixture of 4-iodobenzonitrile (4.5 g, 19.6 mmol), dichlorobis(triphenylphosphine)palladium(II) (0.69 g, 0.98 mmol), copper (1) iodide (0.19 g, 0.98 mmol), triethylamine (11 mL, 78.4 mmol), and THF (24 mL). After stirring for 10 min, the ice bath was removed, and the reaction was allowed to stir for an additional 2 h. The reaction mixture was passed through a pad of silica gel with methylene chloride/ethyl acetate (5:1) as eluant. After evaporating the solvent, the crude product was chromatographed with methylene chloride/ethyl acetate (20:1) as eluant. Evaporation of the solvent, followed by placement under vacuum for 1 h, afforded the pure product 56 (5.2 g, 99%) as an oil. 1H NMR (300 MHz, CDCl3) δ 1.46 (s, 9H), 2.64 (t, 2H), 3.37 (m, 2H), 4.85 (br s, 1H), 7.47 (d, 2H), 7.58 (d, 2H).

Aufarbeitung

  1. temperaturecooled
  2. customargon purged
  3. stirringAfter stirring for 10 min
  4. customthe ice bath was removed
  5. stirringto stir for an additional 2 h
  6. customAfter evaporating the solvent
  7. customthe crude product was chromatographed with methylene chloride/ethyl acetate (20:1) as eluant
  8. customEvaporation of the solvent

Quellen und Nachweise

ORD-Eintrag
ord-5e656e4dfbef4f54b82be3b57cef2ec3
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08846688B2

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