Acetic Acid → Racemic benzyl-(3,3-dimethyl-cyclohexyl)-amine

HRID 905942Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 905942
[CH3:1][C:2]1([CH3:9])[CH2:7][CH2:6][CH2:5][C:4](=O)[CH2:3]1.[CH2:10]([NH2:17])[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C(O)(=O)C>C1C=CC=CC=1.O>[CH2:10]([NH:17][CH:4]1[CH2:5][CH2:6][CH2:7][C:2]([CH3:9])([CH3:1])[CH2:3]1)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Komponenten

7

Edukt 4

HCID 176Acetic AcidHCID 7504BenzylamineHCID 76322Cyclohexanone, 3,3-dimethyl-HCID 5049666Sodium triacetoxyborohydride

Produkt 1

HCID 64469064Racemic benzyl-(3,3-dimethyl-cyclohexyl)-amineAusbeute 19,4 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 241BenzeneLösungsmittelHCID 962WaterLösungsmittel

Versuchsvorschrift

3,3-Dimethylcyclohexanone (3 g, 23.77 mmol) and benzylamine (2.73 mL, 24.96 mmol) were dissolved in benzene (20 mL) and stirred at reflux with continuous removal of H2O for 3 hours. The reaction mixture was allowed to cool to RT and the solvent was evaporated. The imine intermediate was dissolved in DCM (100 mL) and cooled to 0° C. Sodium triacetoxyborohydride (95%, 6.36 g, 28.53 mmol) and acetic acid (1.5 mL, 26.15 mmol) were added. After about 20 minutes the ice bath was removed, and the suspension stirred at RT overnight. The reaction mixture was cooled to 0° C. and saturated aqueous NaHCO3 was added. The layers were separated and the aqueous layer was extracted with DCM. The combined organic layers were washed once more with saturated aqueous NaHCO3, dried (Na2SO4), filtered and evaporated. The remaining yellow oil (5 g) was purified by SiO2 chromatography (300 g SiO2, DCM/(DCM:MeOH:NH4OH 60:10:1) 100 to 87% DCM) to give 1 g of racemic benzyl-(3,3-dimethyl-cyclohexyl)-amine as a light yellow oil (19% yield).

Aufarbeitung

  1. customthe solvent was evaporated
  2. dissolutionThe imine intermediate was dissolved in DCM (100 mL)
  3. temperaturecooled to 0° C
  4. customAfter about 20 minutes the ice bath was removed
  5. stirringthe suspension stirred at RT overnight
  6. temperatureThe reaction mixture was cooled to 0° C.
  7. additionsaturated aqueous NaHCO3 was added
  8. customThe layers were separated
  9. extractionthe aqueous layer was extracted with DCM
  10. washThe combined organic layers were washed once more with saturated aqueous NaHCO3
  11. dry with materialdried (Na2SO4)
  12. filtrationfiltered
  13. customevaporated
  14. customThe remaining yellow oil (5 g) was purified by SiO2 chromatography (300 g SiO2, DCM/(DCM:MeOH:NH4OH 60:10:1) 100 to 87% DCM)

Quellen und Nachweise

ORD-Eintrag
ord-916a3aa1982f48feacd04e914620853b
Quelldatensatz
uspto-grants-2011_09
Patentnummer
US08012974B2

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