Hydrochloric Acid → 9-Benzyl-9-azabicyclo[3.3.1]nonan-3-one

HRID 252146

Reaktionsgleichung

Reaktionsgleichung von HRID 252146
[CH:1](=O)[CH2:2][CH2:3][CH2:4][CH:5]=[O:6].Cl.[CH2:9]([NH2:16])[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.O=[C:18]([CH2:23]C(O)=O)[CH2:19]C(O)=O.C([O-])(=O)C.[Na+].Cl>O>[CH2:9]([N:16]1[CH:3]2[CH2:2][CH2:1][CH2:23][CH:18]1[CH2:19][C:5](=[O:6])[CH2:4]2)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Komponenten

7

Edukt 5

HCID 313Hydrochloric AcidHCID 3485GlutaraldehydeHCID 68328Acetonedicarboxylic acidHCID 517045Sodium AcetateHCID 2724127Benzylammonium chloride

Produkt 1

HCID 4195319-Benzyl-9-azabicyclo[3.3.1]nonan-3-oneAusbeute 54,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

Glutaraldehyde (25% solution in water) (910 mL, 2.4 mol) and benzylamine hydrochloride (344.1 g, 2.4 mol) in water (1050 mL) was cooled to 0° C. 3-Oxopentanedioic acid (350.0 g, 2.4 mol) was added followed by addition of sodium acetate (aq.) (79.7 g in 797 mL water) resulting in formation of a thick orange precipitate. The reaction mixture was heated to 50° C. and stirred at this temperature for 4 h. It was then cooled to ambient temperature and allowed to stand for 24 h. The reaction mixture was acidified to pH2 with 5N aqueous hydrochloric acid (˜150 mL) and the resulting aqueous mixture was washed with diethyl ether (2×500 mL). The aqueous extracts were basified to pH12 with 4N aqueous sodium hydroxide (˜650 mL) and extracted with dichloromethane (6×500 mL). The organic phase was dried (MgSO4) and concentrated under reduced pressure to afford the crude product as a red oil. Purification by chromatography on silica gel with dichloromethane:methanol (49:1, v/v) as eluent afforded 9-benzyl-9-azabicyclo[3.3.1]nonan-3-one (300.0 g, 1.3 mol, 54%) as a pale orange solid.

Aufarbeitung

  1. customresulting in formation of a thick orange precipitate
  2. temperatureIt was then cooled to ambient temperature
  3. waitto stand for 24 h
  4. washthe resulting aqueous mixture was washed with diethyl ether (2×500 mL)
  5. extractionextracted with dichloromethane (6×500 mL)
  6. dry with materialThe organic phase was dried (MgSO4)
  7. concentrationconcentrated under reduced pressure
  8. customto afford the crude product as a red oil
  9. customPurification by chromatography on silica gel with dichloromethane:methanol (49:1

Quellen und Nachweise

ORD-Eintrag
ord-51bb9d7f4cc24d34902dfcebc4f78b68
Quelldatensatz
uspto-grants-2011_01
Patentnummer
US07868017B2

Verknüpfte Notizen

Wird geladen…