Methyl iodide → 1-Cyano-3-methylthio-4-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[c]thiophene

HRID 1385293Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1385293
[C:1]1(=[O:9])[CH2:7][CH2:6][CH2:5][CH2:4][C:3](=O)[CH2:2]1.[H-].[Na+].[C:12](=[S:14])=[S:13].[CH3:15]I.Br[CH2:18][C:19]#[N:20]>CN(C=O)C.O>[C:19]([C:18]1[S:13][C:12]([S:14][CH3:15])=[C:2]2[C:1](=[O:9])[CH2:7][CH2:6][CH2:5][CH2:4][C:3]=12)#[N:20]

Komponenten

8

Edukt 5

HCID 6328Methyl iodideHCID 6348Carbon DisulfideHCID 11534BromoacetonitrileHCID 24758Sodium hydrideHCID 4072367Cycloheptane-1,3-dione

Produkt 1

HCID 211845001-Cyano-3-methylthio-4-oxo-5,6,7,8-tetrahydro-4H-cyclohepta[c]thiopheneAusbeute 32 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

Cycloheptan-1,3-dione (0.5 g, 4 mmol) was dissolved in DMF (10 mL) and cooled to 0° C. Sodium hydride (0.48 g of 60% dispersion in oil, 12 mmol) was added and the suspension stirred at 0-5° C. for 30 min. Carbon disulphide (0.45 g, 6 mmol) was added in one portion and the solution was stirred at 0-5° C. for 30 min. Methyl iodide (0.66 g, 4.4 mmol) was added in one portion and the mixture stirred at room temperature for 30 min. After cooling to 0-5° C., bromoacetonitrile (0.27 mL, 4.4 mmol) was added in one portion and the mixture was stirred at room temperature for 30 min. The mixture was then poured into water, extracted with ethyl acetate and the extracts dried (Na2SO4). After evaporating to dryness, the residue was purified by chromatographed on silica gel, eluting with ethyl acetate:hexane (1:4) to yield the title compound as a pale yellow solid (280 mg, 32%). 1HNMR (360 MHz, CDCl3) δ 1.88-1.96 (4H, m), 2.60 (3H, s), 2.75-2.78 (2H, m), 3.21-3.24 (2H, m). MS (ES+) 296 (M+1).

Aufarbeitung

  1. stirringthe solution was stirred at 0-5° C. for 30 min
  2. stirringthe mixture stirred at room temperature for 30 min
  3. temperatureAfter cooling to 0-5° C.
  4. stirringthe mixture was stirred at room temperature for 30 min
  5. extractionextracted with ethyl acetate
  6. dry with materialthe extracts dried (Na2SO4)
  7. customAfter evaporating to dryness
  8. customthe residue was purified
  9. customby chromatographed on silica gel
  10. washeluting with ethyl acetate:hexane (1:4)

Quellen und Nachweise

ORD-Eintrag
ord-ff07417bf9da4454a823c9f7c14b48d3
Quelldatensatz
uspto-grants-2001_07
Patentnummer
US06262103B1

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