Water → N-benzyl-4-hydroxy-3-oxobutanamide

HRID 526716

Reaktionsgleichung

Reaktionsgleichung von HRID 526716
[CH2:1]([NH:8][C:9](=[O:14])[CH2:10][C:11](=[O:13])[CH3:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.BrBr.O.C([O-])=[O:19].[K+]>ClCCl>[CH2:1]([NH:8][C:9](=[O:14])[CH2:10][C:11](=[O:13])[CH2:12][OH:19])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Komponenten

6

Edukt 4

HCID 962Water2×HCID 24408Bromine2×HCID 70159Acetoacetobenzylamide2×HCID 2735122Potassium Formate

Produkt 1

HCID 71502813N-benzyl-4-hydroxy-3-oxobutanamideAusbeute 38,8 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
7.5 °C

Versuchsvorschrift

To a solution of N-benzyl-3-oxobutanamide (compound A 50 g, 261 mmol) in dichloromethane (350 ml) was added bromine (14.82 ml, 288 mmol) at 0-5° C., then stirred at 20-25° C. for 3 hours (bromine colour disappeared). Water (300 ml) was added to the mixture with stirring, stirred for 10 min. Organic phase was separated, washed with sodium bicarbonate solution, dried, evaporated to dryness (compound B). The solid residue (compound B) dissolved in methanol (900 ml), added potassium formate (44.0 g, 523 mmol) and the mixture was heated under reflux for 2 hours. Methanol was removed on a rotavap, the residue was taken up into ethyl acetate (EA) (500 ml) under reflux, filtered hot, the filter cake washed with warm EA (100 ml). The combined filtrate was cooled to 5-10° C., aged for 1.5 hours. The precipitate was collected, washed with cold EA (50 ml), dried to give 25 g (46.1%) of crude product, light beige. Re-crystallised from water (300 ml), with active carbon (1 g). Filtered hot on celite, cooled in ice, aged for 1 hour, crystals collected, washed with cold water (20 ml), dried on air overnight to give N-benzyl-4-hydroxy-3-oxobutanamide (21 g, 101 mmol, 38.8% yield).

Aufarbeitung

  1. stirringstirred for 10 min
  2. customOrganic phase was separated
  3. washwashed with sodium bicarbonate solution
  4. customdried
  5. customevaporated to dryness (compound B)
  6. dissolutionThe solid residue (compound B) dissolved in methanol (900 ml)
  7. temperaturethe mixture was heated
  8. temperatureunder reflux for 2 hours
  9. customMethanol was removed on a rotavap
  10. temperatureunder reflux
  11. filtrationfiltered hot
  12. washthe filter cake washed with warm EA (100 ml)
  13. customThe precipitate was collected
  14. washwashed with cold EA (50 ml)
  15. customdried
  16. customto give 25 g (46.1%) of crude product
  17. filtrationFiltered hot on celite
  18. temperaturecooled in ice
  19. waitaged for 1 hour
  20. customcrystals collected
  21. washwashed with cold water (20 ml)
  22. customdried on air overnight

Quellen und Nachweise

ORD-Eintrag
ord-c619e5d24af943a4b31ecc31c061d00b
Quelldatensatz
uspto-grants-2016_05
Patentnummer
US09346751B2

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