((1,1-Dimethyl-2-propynyl)oxy)trimethylsilane → 2-Methoxy-5-(4-methyl-4-(trimethylsilyloxy)pent-2-ynoyl)benzonitrile

HRID 1258332Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1258332
[CH3:1][Si:2]([CH3:10])([CH3:9])[O:3][C:4]([CH3:8])([C:6]#[CH:7])[CH3:5].[Li]CCCC.[C:16]([C:18]1[CH:19]=[C:20]([CH:27]=[CH:28][C:29]=1[O:30][CH3:31])[C:21](N(OC)C)=[O:22])#[N:17]>C1COCC1>[CH3:31][O:30][C:29]1[CH:28]=[CH:27][C:20]([C:21](=[O:22])[C:7]#[C:6][C:4]([CH3:8])([O:3][Si:2]([CH3:10])([CH3:9])[CH3:1])[CH3:5])=[CH:19][C:18]=1[C:16]#[N:17]

Komponenten

5

Edukt 3

HCID 87344((1,1-Dimethyl-2-propynyl)oxy)trimethylsilaneHCID 593547633-cyano-N,4-dimethoxy-N-methylbenzamideHCID 178418339Butyllithium

Produkt 1

HCID 593548212-Methoxy-5-(4-methyl-4-(trimethylsilyloxy)pent-2-ynoyl)benzonitrileAusbeute 56 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

To a −78° C. stirred solution of trimethyl(2-methylbut-3-yn-2-yloxy)silane (1.9 g, 12.501 mmol) in dry THF (25 mL), n-BuLi (2.80 mL, 4.50 mmol, 1.6 M in hexane) was added dropwise over 10 minutes under an inert atmosphere. The reaction was stirred for 30 min at −78° C., and then a solution of 3-cyano-N,4-dimethoxy-N-methylbenzamide (1.10 g, 5.01 mmol) in dry THF (10 mL) was added to reaction mixture and stirring was continued for an additional 3 h at −78° C. The reaction mixture was quenched with a saturated NH4Cl solution and extracted with EtOAc (2×50 mL). The combined organic layers were washed with water (20 mL) and brine (20 mL), dried over Na2SO4, filtered and concentrated in vacuo to obtain the crude product. The crude material was purified via silica gel column chromatography eluting with 5% EtOAc in hexanes to afford 2-methoxy-5-(4-methyl-4-(trimethylsilyloxy)pent-2-ynoyl)benzonitrile (0.8 g, 56%) as a pale yellow oil.

Aufarbeitung

  1. additionwas added dropwise over 10 minutes under an inert atmosphere
  2. stirringstirring
  3. waitwas continued for an additional 3 h at −78° C
  4. customThe reaction mixture was quenched with a saturated NH4Cl solution
  5. extractionextracted with EtOAc (2×50 mL)
  6. washThe combined organic layers were washed with water (20 mL) and brine (20 mL)
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customto obtain the crude product
  11. customThe crude material was purified via silica gel column chromatography
  12. washeluting with 5% EtOAc in hexanes

Quellen und Nachweise

ORD-Eintrag
ord-e0563dbee79047e2b278630ea0e1ff39
Quelldatensatz
uspto-grants-2013_06
Patentnummer
US08466148B2

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