Dimethyl Sulfate → (1-Methoxyphenylethylidene)malononitrile

HRID 1736554

Reaktionsgleichung

Reaktionsgleichung von HRID 1736554
[H-].[Na+].[OH:3][C:4]1([CH2:10][CH:11]=[C:12]([C:15]#[N:16])[C:13]#[N:14])[CH:9]=[CH:8][CH:7]=[CH:6][CH2:5]1.[CH3:17]OS(OC)(=O)=O>C1COCC1>[CH3:17][O:3][C:4]1([CH2:10][CH:11]=[C:12]([C:13]#[N:14])[C:15]#[N:16])[CH:5]=[CH:6][CH:7]=[CH:8][CH2:9]1

Komponenten

5

Edukt 3

HCID 6497Dimethyl Sulfate2×HCID 24758Sodium hydride2×HCID 86747658(1-Hydroxyphenylethylidene)malononitrile

Produkt 1

HCID 86747657(1-Methoxyphenylethylidene)malononitrileAusbeute 56,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel3×

Versuchsvorschrift

To a suspension of 60% NaH/mineral oil dispersion (2.9 g, 74.7 mmol) in THF (50 ml) was added dropwise (1-hydroxyphenylethylidene)malononitrile (13.8 g, 74.7 mmol) in THF (75 ml) over 25 minutes, followed by dimethylsulfate (7.1 ml, 74.7 mmol) in THF (50 ml) over 20 minutes. The reaction mixture was stirred at room temperature for 30 minutes, then at reflux for 4 hours. 0.5 equivalents of 60% sodium hydride and dimethylsulfate were added and the reaction mixture was stirred at room temperature for 24 hours. The solvent was removed in vacuo, the residue was partitioned between ether and water, the organic layer was separated and the aqueous layer was extracted with ether (3×150 ml). The combined organic layers were dried over anhydrous MgSO4 and solvent was removed in vacuo. The residue was purified by column chromatography on silica eluting with ethyl acetate/hexanes (1/1) to afford 8.4 g (56%) of (1-methoxyphenylethylidene)malononitrile as an amber liquid.

Aufarbeitung

  1. temperatureat reflux for 4 hours
  2. stirringthe reaction mixture was stirred at room temperature for 24 hours
  3. customThe solvent was removed in vacuo
  4. customthe residue was partitioned between ether and water
  5. customthe organic layer was separated
  6. extractionthe aqueous layer was extracted with ether (3×150 ml)
  7. dry with materialThe combined organic layers were dried over anhydrous MgSO4 and solvent
  8. customwas removed in vacuo
  9. customThe residue was purified by column chromatography on silica eluting with ethyl acetate/hexanes (1/1)

Quellen und Nachweise

ORD-Eintrag
ord-a0e78d52e24647ccba31e03c81e9ad57
Quelldatensatz
uspto-grants-1996_07
Patentnummer
US05541187

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