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L-Phenylalanine → N-[2-[(Acetylthio)methyl]-3,3,3-trifluoro-1-oxopropyl]-L-phenylalanine

HRID 36499
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 36499
[NH2:1][C@H:2]([C:10]([OH:12])=[O:11])[CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.C[Si](N([Si](C)(C)C)[C:18](=[O:23])[C:19](F)(F)F)(C)C.[F:28][C:29]([F:39])([F:38])[CH:30]([CH2:34]C(=O)C)[C:31](Cl)=[S:32].C(OCC)(=[O:42])C>C(#N)C.CO.C(O)(=O)C>[C:18]([S:32][CH2:31][CH:30]([C:29]([F:28])([F:38])[F:39])[C:34]([NH:1][C@H:2]([C:10]([OH:12])=[O:11])[CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)=[O:42])(=[O:23])[CH3:19]
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

8

Edukt 4

HCID 6140L-PhenylalanineHCID 8857Ethyl AcetateHCID 65279N,N-Bis(trimethylsilyl)trifluoroacetamideHCID 543085362-Trifluoromethyl-3-acetylthiopropionyl chloride

Produkt 1

HCID 53713035N-[2-[(Acetylthio)methyl]-3,3,3-trifluoro-1-oxopropyl]-L-phenylalanine

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 176
Acetic Acid
Lösungsmittel
HCID 887MethanolLösungsmittel
HCID 6342AcetonitrileLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A stirred suspension of L-phenylalanine (7.60 g, 46 mmol) in 45 mL of dry acetonitrile under argon was cooled to 0° C. and bis(trimethylsilyl)trifluoroacetamide (24.7 mL, 92 mmol) was added. The reaction mixture was allowed to stir and slowly warm to room temperature. After 4 hours, practically all of the amino acid was in the solution, which was light yellow in color. 2-Trifluoromethyl-3-acetylthio propionyl chloride (4.69 g, 20 mmol), dissolved in 10 mL of acetonitrile, was added dropwise over a period of about 45 minutes at 5° C. and thereafter the reaction mixture was allowed to warm to room temperature and stir overnight. The mixture was evaporated under reduced pressure to give a light yellow oil. The oil was partitioned between water (75 mL) and ethyl acetate (100 mL). The entire mixture was filtered to remove a white precipitate (phenylalanine), and the organic layer was separated. The aqueous phase was extracted once more with 50 mL of ethyl acetate. The combined ethyl acetate extract was washed with brine, dried over anhydrous magnesium sulfate and evaporated to give 20.1 g of the crude mixture of diastereomers as a light yellow solid. A 2.0 g portion of the product was flash chromatographed on silica gel (125:1 silica gel to compound), using ethyl acetate: hexanes:acetic acid, 100:100:1 as the eluent, to yield 0.370 g of the faster eluting diastereomer (isomer A) and 0.383 g of the slower eluting diastereomer (isomer B). The remaining 18.1 g of crude material was flash chromatographed similarly to yield 2.67 g of isomer A and 2.92 g of isomer B. The combined yield of isomer A was 3.04 g as a white crystalline solid, m.p. 183°-185° C., TLC Rf =0.30 (200:100:1 ethyl acetate:hexanes:acetic acid), [α]D =-98.8° (c=1.00, methanol).

Aufarbeitung

  1. temperatureslowly warm to room temperature
  2. additionwas added dropwise over a period of about 45 minutes at 5° C.
  3. temperatureto warm to room temperature
  4. stirringstir overnight
  5. customThe mixture was evaporated under reduced pressure
  6. customto give a light yellow oil
  7. customThe oil was partitioned between water (75 mL) and ethyl acetate (100 mL)
  8. filtrationThe entire mixture was filtered
  9. customto remove a white precipitate (phenylalanine)
  10. customthe organic layer was separated
  11. extractionThe aqueous phase was extracted once more with 50 mL of ethyl acetate
  12. extractionThe combined ethyl acetate extract
  13. washwas washed with brine
  14. dry with materialdried over anhydrous magnesium sulfate
  15. customevaporated
  16. customto give 20.1 g of the crude mixture of diastereomers as a light yellow solid
  17. customchromatographed on silica gel (125:1 silica gel to compound)
  18. customhexanes:acetic acid, 100:100:1 as the eluent, to yield 0.370 g of the
  19. washfaster eluting diastereomer (isomer A) and 0.383 g of the
  20. washslower eluting diastereomer (isomer B)
  21. customchromatographed similarly
  22. customto yield 2.67 g of isomer A and 2.92 g of isomer B

Quellen und Nachweise

ORD-Eintrag
ord-00fa54dba33545b4b8f9d366518a2ca1
Quelldatensatz
uspto-grants-1995_05
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US05414013

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