Hydrazine → tert-butyl (S)-1-((R)-2,2,2-trifluoro-1-(6-hydrazinylpyridin-3-yl)ethyl)pyrrolidin-3-ylcarbamate

HRID 338845Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 338845
Cl[C:2]1[N:7]=[CH:6][C:5]([C@@H:8]([N:13]2[CH2:17][CH2:16][C@H:15]([NH:18][C:19](=[O:25])[O:20][C:21]([CH3:24])([CH3:23])[CH3:22])[CH2:14]2)[C:9]([F:12])([F:11])[F:10])=[CH:4][CH:3]=1.[NH2:26][NH2:27]>C(O)C(C)C>[F:10][C:9]([F:12])([F:11])[C@H:8]([N:13]1[CH2:17][CH2:16][C@H:15]([NH:18][C:19](=[O:25])[O:20][C:21]([CH3:24])([CH3:23])[CH3:22])[CH2:14]1)[C:5]1[CH:6]=[N:7][C:2]([NH:26][NH2:27])=[CH:3][CH:4]=1

Komponenten

4

Edukt 2

HCID 9321HydrazineHCID 86707413tert-butyl (S)-1-((R)-1-(6-chloropyridin-3-yl)-2,2,2-trifluoroethyl)pyrrolidin-3-ylcarbamate

Produkt 1

HCID 86707414tert-butyl (S)-1-((R)-2,2,2-trifluoro-1-(6-hydrazinylpyridin-3-yl)ethyl)pyrrolidin-3-ylcarbamateAusbeute 100,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6560IsobutanolLösungsmittel

Versuchsvorschrift

A solution of tert-butyl (S)-1-((R)-1-(6-chloropyridin-3-yl)-2,2,2-trifluoroethyl)pyrrolidin-3-ylcarbamate (68.5 g, 180.4 mmol) and anhydrous hydrazine (56.61 mL, 1804 mmol) in i-BuOH (80 mL) was stirred at 106° C. in a sealed flask for 16 hours. After cooling to ambient temperature, the solvent was removed under reduced pressure. The residue was partitioned in ethyl acetate (800 mL) and water (100 mL). The organic layer was separated, washed with brine, dried (sodium sulfate), filtered and concentrated under reduced pressure to give tert-butyl (S)-1-((R)-2,2,2-trifluoro-1-(6-hydrazinylpyridin-3-yl)ethyl)pyrrolidin-3-ylcarbamate (68.1 g, 95.6%) as white foam solid. Enantiomeric excess was determined by chiral HPLC (Chiralcel OD-H, 90% hexane/10% (1:1 MeOH/EtOH) at 1.0 mL/min, >99% d.e. (R,S)-diastereomer).

Aufarbeitung

  1. customthe solvent was removed under reduced pressure
  2. customThe residue was partitioned in ethyl acetate (800 mL)
  3. customThe organic layer was separated
  4. washwashed with brine
  5. dry with materialdried (sodium sulfate)
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-18487635e55440b4aa01771103956739
Quelldatensatz
uspto-grants-2014_11
Patentnummer
US08889704B2

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