Sulfuric Acid → (2S)-5-[(benzyloxy)amino]-2-cyanopiperidine

HRID 517669

Reaktionsgleichung

Reaktionsgleichung von HRID 517669
S(=O)(=O)(O)O.[CH2:6]([O:13][N:14]=[C:15]1[CH2:20][NH:19][C@H:18]([C:21]#[N:22])[CH2:17][CH2:16]1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C(=O)([O-])O.[K+]>C(OCC)(=O)C>[CH2:6]([O:13][NH:14][CH:15]1[CH2:20][NH:19][C@H:18]([C:21]#[N:22])[CH2:17][CH2:16]1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Komponenten

6

Edukt 4

HCID 1118Sulfuric AcidHCID 516893Potassium BicarbonateHCID 5049666Sodium triacetoxyborohydrideHCID 90088575(2S)-5-[(benzyloxy)imino]-2-cyanopiperidine

Produkt 1

HCID 117599345(2S)-5-[(benzyloxy)amino]-2-cyanopiperidineAusbeute 88 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
25 °C

Versuchsvorschrift

Sulphuric acid (11.7 ml, 0.217 mol) was slowly added to a stirred solution of (2S)-5-[(benzyloxy)imino]-2-cyanopiperidine (IX) (10 gm, 0.0436 mol, prepared according to the procedure described in step 6) in ethyl acetate (150 ml) at −10° C. After 10 minutes of stirring, sodium triacetoxy borohydride (NaHB(OOCCH3)3) (11.7 gm, 0.0519 mol, 95% purity) was added in small portions while maintaining temperature below −5° C. After completion of the addition, stirring was further continued for 2 hour at the same temperature. The pH of the reaction mixture was adjusted to about pH 7 by using 30% aqueous potassium hydrogen carbonate solution. The mixture was allowed to warm to 25° C. and the reaction mixture was filtered under suction. The organic layer was separated and the aqueous layer extracted with fresh ethyl acetate (50 ml). The combined organic layer was washed with water (50 ml) and brine (50 ml), dried over anhydrous sodium sulphate and the solvent evaporated under reduced pressure to obtain 8.88 gm of (2S)-5-[(benzyloxy)amino]-2-cyanopiperidine (X) as an oil, in 88% yield. This was used as such for the next step without further purification.

Aufarbeitung

  1. customprepared
  2. customat −10° C
  3. temperaturewhile maintaining temperature below −5° C
  4. additionAfter completion of the addition
  5. stirringstirring
  6. waitwas further continued for 2 hour at the same temperature
  7. filtrationthe reaction mixture was filtered under suction
  8. customThe organic layer was separated
  9. extractionthe aqueous layer extracted with fresh ethyl acetate (50 ml)
  10. washThe combined organic layer was washed with water (50 ml) and brine (50 ml)
  11. dry with materialdried over anhydrous sodium sulphate
  12. customthe solvent evaporated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-11cd144b00c34a06b286f049aa7d3018
Quelldatensatz
uspto-grants-2015_08
Patentnummer
US09115131B2

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