Reaction #92981

ord-18bde555835b47f78c6ab8bfa5bd8bba

Reaction equation

CCOC(C)=O
ethyl acetate
CC[C@H]1C[C@H]2[C@@H]3CCC4=CC(=O)CC[C@@H]4[C@H]3CC[C@]2(C)[C@H]1O
16β-ethyl-17β-hydroxy-4-estren-3-one
CN(C)c1ccccc1
N,N-dimethylaniline
O=C(Br)CBr
bromoacetyl bromide
→
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
above-identified compound
Yield 74.6%
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
Yield 74.6%

Reactants

CCOC(C)=O
ethyl acetate
CC[C@H]1C[C@H]2[C@@H]3CCC4=CC(=O)CC[C@@H]4[C@H]3CC[C@]2(C)[C@H]1O
16β-ethyl-17β-hydroxy-4-estren-3-one
CN(C)c1ccccc1
N,N-dimethylaniline
O=C(Br)CBr
bromoacetyl bromide

Reagents

None

Solvents

ClCCl
dichloromethane
ClCCl
dichloromethane

Conditions

Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    Temperaturewith ice-cooling
  2. 2
    workup.STIRRINGThe mixture is stirred with ice-
  3. 3
    WashThe mixture is washed with 10% cold sulfuric acid (three times), water and saturated aqueous sodium chloride solution in that order
  4. 4
    Dryingdried over anhydrous sodium sulfate
  5. 5
    workup.DISTILLATIONThe solvent is then distilled off under reduced pressure
  6. 6
    OtherThe residue is recrystallized from diisopropyl ether-petroleum ether (1:1)

Procedure

In 40 ml of dichloromethane are dissolved 4.5 g of 16β-ethyl-17β-hydroxy-4-estren-3-one and 1.8 g of N,N-dimethylaniline and, with ice-cooling and stirring, a solution of 3.5 g of bromoacetyl bromide in 5 ml of dichloromethane is added dropwise to the above solution. The mixture is stirred with ice-cooling for 30 minutes and at room temperature (15°-25° C.) for 5 hours, and 200 ml of ethyl acetate is added. The mixture is washed with 10% cold sulfuric acid (three times), water and saturated aqueous sodium chloride solution in that order and dried over anhydrous sodium sulfate. The solvent is then distilled off under reduced pressure. The residue is recrystallized from diisopropyl ether-petroleum ether (1:1) to give 4.7 g of the above-identified compound as colorless crystals.

Source

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