Hydrochloric Acid → Ethyl 4-(2-azidoethoxy)-3-oxobutanoate

HRID 652075Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 652075
[N:1]([CH2:4][CH2:5][OH:6])=[N+:2]=[N-:3].[H-].[Na+].Cl[CH2:10][C:11](=[O:18])[CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14].Cl>O1CCCC1.C(O)C.O>[N:1]([CH2:4][CH2:5][O:6][CH2:10][C:11](=[O:18])[CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14])=[N+:2]=[N-:3]

Komponenten

8

Edukt 4

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 69484Ethyl 4-chloroacetoacetateHCID 1231182-Azidoethanol

Produkt 1

HCID 13663141Ethyl 4-(2-azidoethoxy)-3-oxobutanoate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 702EthanolLösungsmittelHCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel3×

Versuchsvorschrift

A solution of 2-azidoethanol (160 g) in tetrahydrofuran (300 ml) was added over 40 minutes to a suspension of sodium hydride (114 g; 80% dispersion in oil) in tetrahydrofuran (500 ml). The mixture was stirred at room temperature for 1 hour and the ice-cooled solution treated with a solution of ethyl 4-chloroacetoacetate (276 g) in tetrahydrofuran (250 ml) dropwise over 2 hours. The mixture was stirred at room temperature for 16 hours, diluted with ethanol (150 ml), and the pH adjusted to 6-7 with 4M hydrochloric acid. Sufficient water was added to dissolve the solid present and the layers were separated. The organic layer was evaporated and the residue diluted with water (600 ml) and evaporated. The residue was partitioned between ethyl acetate and water and the aqueous layer extracted twice with ethyl acetate. The combined ethyl acetate extracts were dried (MgSO4) and evaporated to give ethyl 4-(2-azidoethoxy)acetoacetate as a brown oil, which was shown by g.l.c. to be 73% pure. A mixture of this crude product and ammonium acetate (92.3 g) in ethanol (600 ml) was heated under reflux for 1 hour, allowed to cool to room temperature, and treated with methyl 2-(2-chlorobenzylidene)acetoacetate (286.6 g). The mixture was heated under reflux for 5.5 hours and then evaporated. The residue was stirred with methanol (1.5 l) for 16 hours and the resulting solid collected, washed twice with methanol, dried, and recrystallised from methanol to give the title compound (78 g), m.p. 145°-146°.

Aufarbeitung

  1. stirringThe mixture was stirred at room temperature for 16 hours
  2. dissolutionto dissolve the solid present
  3. customthe layers were separated
  4. customThe organic layer was evaporated
  5. additionthe residue diluted with water (600 ml)
  6. customevaporated
  7. customThe residue was partitioned between ethyl acetate and water
  8. extractionthe aqueous layer extracted twice with ethyl acetate
  9. dry with materialThe combined ethyl acetate extracts were dried (MgSO4)
  10. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-3657298e4d7d42e7ac9a35cc2b25cfd6
Quelldatensatz
uspto-grants-1987_06
Patentnummer
US04670449

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