Sodium Bromide → N-benzyl-N-(tert-butoxycarbonyl)-L-phenylalaninal

HRID 23237

Reaktionsgleichung

Reaktionsgleichung von HRID 23237
[C:1]([O:5][C:6]([N:8]([CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C@H:9]([CH2:17][OH:18])[CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].CC1(C)N([O])C(C)(C)CCC1.[Br-].[Na+].C(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1.O.C(OCC)(=O)C>[C:1]([O:5][C:6]([N:8]([CH2:19][C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)[C@H:9]([CH:17]=[O:18])[CH2:10][C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Komponenten

8

Edukt 4

HCID 253881Sodium BromideHCID 516892Sodium BicarbonateHCID 2724126TempoHCID 15434535N-(t-Butoxycarbonyl)-N-benzyl-L-phenylalaninol

Produkt 1

HCID 11099858N-benzyl-N-(tert-butoxycarbonyl)-L-phenylalaninalAusbeute 100,3 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 1140TolueneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a solution of 0.32 g (0.94 mmoles) of N-(t-Butoxycarbonyl)-N-benzyl-L-phenylalaninol from Example 17 in 2.8 mL of toluene was added 2.4 mg (0.015 mmoles) of 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical (TEMPO), 0.1 g (0.97 mmoles) of sodium bromide, 2.8 mL of ethyl acetate and 0.34 mL of water. The mixture was cooled to 0° C. and an aqueous solution of 4.2 mL of 5% household bleach containing 0.23 g (3.0 mL, 2.738 mmoles) of sodium bicarbonate was added slowly over 30 minutes. The mixture was stirred at 0° C. for 10 minutes. Three more additions (0.4 mL each) of bleach was added followed by stirring for 10 minutes after each addition to consume all the stating material. The two phase mixture was allowed to separate. The aqueous layer was extracted twice with 8 mL of toluene. The combined organic layer was washed with 1.25 mL of a solution containing 0.075 g of potassium iodide, sodium bisulfate (0.125 g) and water (1.1 mL), 1.25 mL of 10% aqueous sodium thiosulfate solution, 1.25 mL of pH 7 phosphate buffer and 1.5 mL of brine solution. The organic solution was dried over magnesium sulfate, filtered and concentrated under reduced pressure to give 0.32 g (100% yield) of N-(t-Butoxycarbonyl)-N-benzyl-L-phenylalaninal.

Aufarbeitung

  1. additionwas added slowly over 30 minutes
  2. additionThree more additions (0.4 mL each) of bleach was added
  3. stirringby stirring for 10 minutes
  4. additionafter each addition
  5. customto consume all the stating material
  6. customto separate
  7. extractionThe aqueous layer was extracted twice with 8 mL of toluene
  8. washThe combined organic layer was washed with 1.25 mL of a solution
  9. additioncontaining 0.075 g of potassium iodide, sodium bisulfate (0.125 g) and water (1.1 mL), 1.25 mL of 10% aqueous sodium thiosulfate solution, 1.25 mL of pH 7 phosphate buffer and 1.5 mL of brine solution
  10. dry with materialThe organic solution was dried over magnesium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-cd584cd671de40ce934aa9b679127836
Quelldatensatz
uspto-grants-2005_02
Patentnummer
US06849760B2

Verknüpfte Notizen

Wird geladen…