Sulfuric Acid → Dipyranyl ethylmalonate

HRID 1742531

Reaktionsgleichung

Reaktionsgleichung von HRID 1742531
[CH2:1]([CH:3]([C:7]([OH:9])=[O:8])[C:4]([OH:6])=[O:5])[CH3:2].[O:10]1[CH:15]=[CH:14][CH2:13][CH2:12][CH2:11]1.S(=O)(=O)(O)O.[H-].[Na+].[C:23]1([C:29]2[CH:33]=[C:32](C(Cl)=O)[O:31]N=2)[CH:28]=CC=CC=1>O1CCCC1.O.C(O)(=O)C.C1C=CC=CC=1>[CH2:1]([CH:3]([C:7]([O:9][CH:32]1[CH:33]=[CH:29][CH:23]=[CH:28][O:31]1)=[O:8])[C:4]([O:6][CH:15]1[CH:14]=[CH:13][CH:12]=[CH:11][O:10]1)=[O:5])[CH3:2]

Komponenten

10

Edukt 5

HCID 1118Sulfuric AcidHCID 80803,4-dihydro-2H-pyranHCID 11756Ethylmalonic acidHCID 24758Sodium hydrideHCID 143973243-Phenylisoxazole-5-carbonyl chloride

Produkt 1

HCID 19976934Dipyranyl ethylmalonate

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 176Acetic AcidLösungsmittelHCID 241BenzeneLösungsmittelHCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

To 130 ml of benzene, were added 12.9 g (97.7 mmol) of ethylmalonic acid, 20.2 g (240.5 mmol) of 3,4-dihydropyran and 2 droplets of concentrated sulfuric acid. They were reacted for 1 hour under ice cooling, whereby dipyranyl ethylmalonate was prepared. The reaction mixture was added with 4.7 g (117.5 mmol) of 60% sodium hydride, followed by heating under stirring at 50° C. for 5 hours. A solution of 15.0 g (79.4 mmol) of 3-phenylisoxazole-5-carboxylic acid chloride, which had been synthesized above in the procedure (3), in 70 ml of tetrahydrofuran was added under ice cooling to the above-prepared reaction mixture. The mixture thus obtained was then subjected to a reaction at room temperature for 12 hours. The reaction mixture was added with 20 ml of acetic acid and then heated under reflux for 8 hours. The reaction mixture so obtained was poured into water and then extracted with benzene. The organic layer was washed successively with water, an aqueous solution of sodium hydrogencarbonate and saturated saline, and was then dried over anhydrous sodium sulfate. After the benzene was distilled off, hexane was added into the residue. Crystals precipitated was collected by filtration, so that 3-phenyl-5-butyrylisoxazole was obtained. Analytical results of the crystals obtained: Yield: 14.6 g (85.6%). Melting point: 90°-92° C.

Aufarbeitung

  1. customThey were reacted for 1 hour under ice cooling
  2. temperatureby heating
  3. additionwas added under ice cooling to the above-prepared reaction mixture
  4. customThe mixture thus obtained
  5. customwas then subjected to a reaction at room temperature for 12 hours
  6. temperatureheated
  7. temperatureunder reflux for 8 hours
  8. customThe reaction mixture so obtained
  9. extractionextracted with benzene
  10. washThe organic layer was washed successively with water
  11. dry with materialan aqueous solution of sodium hydrogencarbonate and saturated saline, and was then dried over anhydrous sodium sulfate
  12. distillationAfter the benzene was distilled off
  13. additionhexane was added into the residue
  14. customCrystals precipitated
  15. filtrationwas collected by filtration, so that 3-phenyl-5-butyrylisoxazole
  16. customwas obtained
  17. customAnalytical results of the crystals
  18. customobtained

Quellen und Nachweise

ORD-Eintrag
ord-2e57c0dabc8a4e23b817e588fcc4babe
Quelldatensatz
uspto-grants-1994_08
Patentnummer
US05338857

Verknüpfte Notizen

Wird geladen…