Tetrahydrofuran → Benzyl [4-(4-iodophenyl)but-3-yn-1-yl]carbamate

HRID 254364Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 254364
C1COCC1.I[C:7]1[CH:12]=[CH:11][C:10]([I:13])=[CH:9][CH:8]=1.[CH2:14]([O:21][C:22](=[O:28])[NH:23][CH2:24][CH2:25][C:26]#[CH:27])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>[Cu]I.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.C(N(CC)CC)C>[CH2:14]([O:21][C:22](=[O:28])[NH:23][CH2:24][CH2:25][C:26]#[C:27][C:7]1[CH:12]=[CH:11][C:10]([I:13])=[CH:9][CH:8]=1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Komponenten

7

Edukt 3

HCID 8028TetrahydrofuranHCID 12208p-DiiodobenzeneHCID 21185506HCID 21185506, Verbindung

Produkt 1

HCID 59750570Benzyl [4-(4-iodophenyl)but-3-yn-1-yl]carbamateAusbeute 86 %

Reagenzien, Katalysatoren, Lösungsmittel 3

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

Versuchsvorschrift

To a mixture of anhydrous THF and triethylamine (24 mL, 2/1, v/v) were sequentially added 1,4-diiodobenzene (2.03 g, 6.15 mmol) and copper (1) iodide (0.094 g, 0.246 mmol). The mixture was stirred at room temperature for 15 min. The flask was then evacuated and re-filled with Argon. The procedure was repeated three more times to ensure no oxygen remained. The catalyst, dichlorobis(triphenylphosphine)palladium(II) (0.173 g, 0.246 mmol) was added into the mixture under Argon protection. The other starting material, but-3-ynylcarbamic acid benzyl ester (0.50 g, 2.46 mmol), dissolved in TBF (8 mL) was added dropwise over 6 hours. The newly formed reaction mixture was further stirred at room temperature overnight. The solid in the reaction mixture was vacuum filtered. The filtrate was concentrated. The residue was re-dissolved in dichloromethane and purified by column chromatography, eluting with a mixture of ethyl acetate (0-12%) and hexanes (100-88%) to afford the product 210 (0.852 g, 86%) as an off-white solid. 1H NMR (300 MHz, CDCl3): δ 2.61 (t, J=6.4 Hz, 2H), 3.44 (t, J=6.4 Hz, 2H), 5.07 (br s, 1H), 5.12 (s, 2H), 7.10 (d, J=8.3 Hz, 2H), 7.35 (m, 5H), 7.63 (d, J=8.3 Hz, 2H). m/z (APCI) 405 [C18H16NO2+H]+.

Aufarbeitung

  1. customThe flask was then evacuated
  2. additionre-filled with Argon
  3. additionwas added dropwise over 6 hours
  4. customThe newly formed reaction mixture
  5. stirringwas further stirred at room temperature overnight
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated
  8. dissolutionThe residue was re-dissolved in dichloromethane
  9. custompurified by column chromatography
  10. washeluting with a mixture of ethyl acetate (0-12%) and hexanes (100-88%)

Quellen und Nachweise

ORD-Eintrag
ord-c3efebc057b14efc9561427c8c3e1cf1
Quelldatensatz
uspto-grants-2011_01
Patentnummer
US07875619B2

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