6-Methoxy-alpha-tetralone → 1-Naphthalenecarbonitrile, 3,4-dihydro-6-methoxy-

HRID 6387

Reaktionsgleichung

Reaktionsgleichung von HRID 6387
C[Si]([C:5]#[N:6])(C)C.[CH3:7][O:8][C:9]1[CH:14]=[CH:13][C:12]2[C:15]([CH2:17][CH2:18][CH2:19][C:11]=2[CH:10]=1)=O.[C-]#N.[Li+]>O1CCCC1.CN(C)C=O>[C:5]([C:15]1[C:12]2[C:11](=[CH:10][C:9]([O:8][CH3:7])=[CH:14][CH:13]=2)[CH2:19][CH2:18][CH:17]=1)#[N:6]

Komponenten

6

Edukt 3

HCID 141126-Methoxy-alpha-tetraloneHCID 75478Lithium cyanideHCID 82115Trimethylsilyl cyanide

Produkt 1

HCID 30144661-Naphthalenecarbonitrile, 3,4-dihydro-6-methoxy-Ausbeute 60,4 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6228DimethylformamideLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

Trimethylsilylcyanide (50.0 g, 510 mmol) was added to a suspension of 75.0 g (430 mmol) of 6-methoxy-α-tetralone (commercially available from Aldrich Chemical Company) in 75 mL of anhydrous tetrahydrofuran (THF) at ambient temperature. Lithium cyanide (100 mL of a 0.5M solution in N,N-dimethylformamide (DMF) was added to the resultant mixture in one portion. The reaction mixture was stirred at ambient temperature for 1.5 h and then the THF was removed under reduced pressure. The concentrate was partitioned between diethyl ether and water (5:1 v/v). The aqueous layer was extracted with diethyl ether and the combined organic extract was washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was dissolved in 400 mL of anhydrous toluene, containing 15 g of p-toluenesulfonic acid, previously refluxed in order to remove residual water by azeotropic distillation. The mixture was heated at reflux (with a Dean Stark trap) for 1 h. The resultant solution was cooled to ambient temperature and washed with cold 1N aqueous sodium hydroxide solution. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The residue was purified on silica gel eluted with 10% ethyl acetate in hexane to afford 48.09 g (60% yield) of the title compound. The physical properties of the product were identical to the properties reported for this compound by F. Z. Basha, et al. in J. Organic Chemistry, 50: 4160-2 (1985).

Aufarbeitung

  1. customthe THF was removed under reduced pressure
  2. customThe concentrate was partitioned between diethyl ether and water (5:1 v/v)
  3. extractionThe aqueous layer was extracted with diethyl ether
  4. extractionthe combined organic extract
  5. washwas washed with brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. dissolutionThe residue was dissolved in 400 mL of anhydrous toluene
  10. additioncontaining 15 g of p-toluenesulfonic acid
  11. temperaturepreviously refluxed in order
  12. customto remove residual water
  13. distillationby azeotropic distillation
  14. temperatureThe mixture was heated
  15. temperatureat reflux (with a Dean Stark trap) for 1 h
  16. temperatureThe resultant solution was cooled to ambient temperature
  17. washwashed with cold 1N aqueous sodium hydroxide solution
  18. customThe organic layer was separated
  19. dry with materialdried over anhydrous magnesium sulfate
  20. filtrationfiltered
  21. concentrationconcentrated in vacuo
  22. customThe residue was purified on silica gel
  23. washeluted with 10% ethyl acetate in hexane

Quellen und Nachweise

ORD-Eintrag
ord-534cc09434c845448a5acfd9ab4503ac
Quelldatensatz
uspto-grants-1993_09
Patentnummer
US05248677

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