1-Hexyne → HCID 68534753, Verbindung

HRID 1992870Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1992870
[CH3:1][O:2][C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5](OS(C(F)(F)F)(=O)=O)[CH:4]=1.C(N(C(C)C)CC)(C)C.[CH:30]#[C:31][CH2:32][CH2:33][CH2:34][CH3:35].[NH4+].[Cl-]>CN(C=O)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:30]([C:5]1[CH:4]=[C:3]([O:2][CH3:1])[CH:12]=[CH:11][C:6]=1[C:7]([O:9][CH3:10])=[O:8])#[C:31][CH2:32][CH2:33][CH2:34][CH3:35]

Komponenten

8

Edukt 4

HCID 127321-HexyneHCID 25517Ammonium ChlorideHCID 81531DiisopropylethylamineHCID 10710352Methyl 4-methoxy-2-(trifluoromethylsulfonyloxy)benzoate

Produkt 1

HCID 68534753HCID 68534753, VerbindungAusbeute 98 %

Reagenzien, Katalysatoren, Lösungsmittel 3

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

Versuchsvorschrift

To a degassed solution of methyl 4-(methyloxy)-2-{[(trifluoromethyl)sulfonyl]oxy}benzoate (77) (0.72 g, 2.30 mmol), Pd(PPh3)2Cl2 (0.16 g, 0.23 mmol), CuI (44 mg, 0.23 mmol), diisopropylethylamine (1.41 mL, 8.02 mmol) in DMF (10 mL) at room temperature was added 1-hexyne (0.55 mL, 4.60 mmol). The mixture was stirred at room temperature overnight. Poured into saturated aqueous NH4Cl (15 mL), the mixture was extracted with EtOAc. The combined organic extract was washed with water, brine, dried over Na2SO4, filtered, and the filtrate was concentrated to give the crude product as a dark brown oil. The crude product was purified by flash chromatography over SiO2 eluted with a gradient from hexanes to 5% EtOAc in hexanes to give 0.55 g (98%) of 78 as a light brown oil. 1H NMR (400 MHz, CDCl3): δ 0.95 (t, J=7.2 Hz, 3H), 1.45-1.58 (m, 2H), 1.60-1.70 (m, 2H), 2.48 (t, J=7.2 Hz, 2H), 3.83 (s, 3H), 3.87 (s, 3H), 6.82 (dd, J1=8.9 Hz, J2=2.6 Hz, 1H), 6.98 (d, J=2.5 Hz, 1H), 7.88 (d, J=8.8 Hz, 1H).

Aufarbeitung

  1. extractionthe mixture was extracted with EtOAc
  2. extractionThe combined organic extract
  3. washwas washed with water, brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated
  7. customto give the crude product as a dark brown oil
  8. customThe crude product was purified by flash chromatography over SiO2
  9. washeluted with a gradient from hexanes to 5% EtOAc in hexanes

Quellen und Nachweise

ORD-Eintrag
ord-2957a998d06c4fa3a7f990b2702d8f5c
Quelldatensatz
uspto-grants-2010_01
Patentnummer
US07649093B2

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