Reaktion #93016

ord-372864b4d00b4392ab44102684528265

Reaktionsgleichung

CC[C@H]1C[C@H]2[C@@H]3CCC4=CC(=O)CC[C@@H]4[C@H]3CC[C@]2(C)[C@H]1OC(=O)CBr
16β-ethyl-17β-bromoacetoxy-4-estren-3-one
CC(C)C[C@H](NC(=O)OC(C)(C)C)C(=O)O
N-t-butoxycarbonylleucine
CC(C)(C)[O-].[K+]
potassium t-butoxide
O
water
→
CC[C@H]1C[C@H]2[C@@H]3CCC4=CC(=O)CC[C@@H]4[C@H]3CC[C@]2(C)[C@H]1OC(=O)COC(=O)[C@H](CC(C)C)NC(=O)OC(C)(C)C
above-identified compound
Ausbeute 80.5%
CC[C@H]1C[C@H]2[C@@H]3CCC4=CC(=O)CC[C@@H]4[C@H]3CC[C@]2(C)[C@H]1OC(=O)COC(=O)[C@H](CC(C)C)NC(=O)OC(C)(C)C
16β-Ethyl-17β-(N-t-butoxycarbonylleucyl)oxyacetoxy-4-estren-3-one
Ausbeute 80.5%

Edukte

CC[C@H]1C[C@H]2[C@@H]3CCC4=CC(=O)CC[C@@H]4[C@H]3CC[C@]2(C)[C@H]1OC(=O)CBr
16β-ethyl-17β-bromoacetoxy-4-estren-3-one
CC(C)C[C@H](NC(=O)OC(C)(C)C)C(=O)O
N-t-butoxycarbonylleucine
CC(C)(C)[O-].[K+]
potassium t-butoxide
O
water

Reagenzien

Keine

Lösungsmittel

CC(C)=O
acetone

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    workup.ADDITIONare added
  2. 2
    TemperaturThe mixture is refluxed for 12 hours
  3. 3
    workup.DISTILLATIONThe solvent is then distilled off under reduced pressure
  4. 4
    Extraktionthe residue is extracted with 150 ml of ethyl acetate
  5. 5
    SonstigeThe organic layer is separated
  6. 6
    Waschenwashed with water and saturated aqueous sodium chloride solution
  7. 7
    Trocknendried over anhydrous magnesium sulfate
  8. 8
    workup.DISTILLATIONThe solvent is distilled off under reduced pressure
  9. 9
    WaschenAfter serial passage of diisopropyl ether-n-hexane mixtures (1:3, 400 ml and 5:2, 750 ml), elution
  10. 10
    workup.ADDITIONis carried out with 1000 ml of a 4:1 mixture of the same solvents
  11. 11
    SonstigeThe eluate is evaporated under reduced pressure
  12. 12
    Sonstigeto remove the solvent

Vorschrift

In 40 ml of acetone is dissolved 1.2 g of N-t-butoxycarbonylleucine, and 1.2 g of potassium t-butoxide and 8 ml of water are added, followed by addition of 1.1 g of 16β-ethyl-17β-bromoacetoxy-4-estren-3-one. The mixture is refluxed for 12 hours. The solvent is then distilled off under reduced pressure and the residue is extracted with 150 ml of ethyl acetate. The organic layer is separated, washed with water and saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure and the residue is subjected to column chromatography. After serial passage of diisopropyl ether-n-hexane mixtures (1:3, 400 ml and 5:2, 750 ml), elution is carried out with 1000 ml of a 4:1 mixture of the same solvents. The eluate is evaporated under reduced pressure to remove the solvent, giving 1.2 g of the above-identified compound as a colorless viscous oil.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US04609650uspto-grants-1986_09