Cesium carbonate → ((E)-5-(3-methoxyphenyl)pent-4-en-1-ynyl)trimethylsilane

HRID 1972273

Reaktionsgleichung

Reaktionsgleichung von HRID 1972273
C(O[CH2:5][CH:6]=[CH:7][C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([O:14][CH3:15])[CH:9]=1)(=O)C.[CH3:16][Si:17]([CH3:24])([CH3:23])[C:18]#[C:19]C(O)=O.C(=O)([O-])[O-].[Cs+].[Cs+]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1(C)C=CC=CC=1>[CH3:15][O:14][C:10]1[CH:9]=[C:8](/[CH:7]=[CH:6]/[CH2:5][C:19]#[C:18][Si:17]([CH3:24])([CH3:23])[CH3:16])[CH:13]=[CH:12][CH:11]=1

Komponenten

6

Edukt 3

HCID 10796Cesium carbonateHCID 27608633-(Trimethylsilyl)propiolic AcidHCID 687029733-Methoxycinnamyl acetate

Produkt 1

HCID 59485813((E)-5-(3-methoxyphenyl)pent-4-en-1-ynyl)trimethylsilaneAusbeute 42 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
75 °C

Versuchsvorschrift

To a dried 40 mL scintillation vial fitted with a Teflon coated cap is added 3-methoxycinnamyl acetate (619 mg, 3.0 mmol), toluene (20 mL), 3-(trimethylsilyl)propiolic acid (512 mg, 3.6 mmol), cesium carbonate (1.17 g, 3.6 mmol), and tetrakis(triphenylphosphine)palladium (0) (346 mg, 0.3 mmol, 10 mol %). The vessel is evacuated and back-filled with Argon and then heated to 75° C. for 18 h. Upon cooling to room temperature, the reaction mixture is quenched with H2O (5 mL) and extracted with diethyl ether (2×10 mL). The combined organics are washed with brine, dried over MgSO4, filtered, and concentrated. The crude oil is purified by flash chromatography (12 g RediSep flash cartridge, hexanes to 1.5% ethyl acetate/hexanes) to give 307 mg (42%) of ((E)-5-(3-methoxyphenyl)pent-4-en-1-ynyl)trimethylsilane as an oil. 1H NMR (acetone-d6, 400 MHz) δ 7.23 (d, J=8.1 Hz, 1H), 6.99-6.97 (m, 2H), 6.80 (m, 1H), 6.65 (dt, J=15.7, 1.7 Hz, 1H), 6.26 (dt, J=15.7, 5.7 Hz, 1H), 3.8 (s, 3H), 3.19 (dd, J=5.7, 1.8 Hz, 2H), 0.16 (s, 9H). Reference: Tunge, J. A.; rayabarapu, D. K. J. Am. Chem. Soc. 2005, 127, 13510-13511.

Aufarbeitung

  1. customcap
  2. customThe vessel is evacuated
  3. additionback-filled with Argon
  4. temperatureUpon cooling to room temperature
  5. customthe reaction mixture is quenched with H2O (5 mL)
  6. extractionextracted with diethyl ether (2×10 mL)
  7. washThe combined organics are washed with brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe crude oil is purified by flash chromatography (12 g RediSep flash cartridge, hexanes to 1.5% ethyl acetate/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-6e26de0eaeab4542b0e032f02b68ab15
Quelldatensatz
uspto-grants-2013_04
Patentnummer
US08431607B2

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