N,N-Dimethylaniline → 16beta-Ethyl-17beta-bromoacetoxy-4-estren-3-one

HRID 64703

Reaction equation

HRID 64703 reaction equation
[CH2:1]([C@H:3]1[CH2:8][C@H:7]2[C@H:9]3[C@H:18]([CH2:19][CH2:20][C@:5]2([CH3:6])[C@H:4]1[OH:22])[C@@H:17]1[C:12](=[CH:13][C:14](=[O:21])[CH2:15][CH2:16]1)[CH2:11][CH2:10]3)[CH3:2].CN(C)C1C=CC=CC=1.[Br:32][CH2:33][C:34](Br)=[O:35].C(OCC)(=O)C>ClCCl>[CH2:1]([C@H:3]1[CH2:8][C@H:7]2[C@H:9]3[C@H:18]([CH2:19][CH2:20][C@:5]2([CH3:6])[C@H:4]1[O:22][C:34](=[O:35])[CH2:33][Br:32])[C@@H:17]1[C:12](=[CH:13][C:14](=[O:21])[CH2:15][CH2:16]1)[CH2:11][CH2:10]3)[CH3:2]

Participants

6

Reactant 4

HCID 949N,N-DimethylanilineHCID 8857Ethyl AcetateHCID 61147Bromoacetyl bromideHCID 443947Oxendolone

Product 1

HCID 1559376416beta-Ethyl-17beta-bromoacetoxy-4-estren-3-oneYield 74.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

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.

Workup

  1. temperaturewith ice-cooling
  2. stirringThe mixture is stirred with ice-
  3. washThe mixture is washed with 10% cold sulfuric acid (three times), water and saturated aqueous sodium chloride solution in that order
  4. dry with materialdried over anhydrous sodium sulfate
  5. distillationThe solvent is then distilled off under reduced pressure
  6. customThe residue is recrystallized from diisopropyl ether-petroleum ether (1:1)

Sources & evidence

ORD record
ord-18bde555835b47f78c6ab8bfa5bd8bba
Source dataset
uspto-grants-1986_09
Patent number
US04609650

Linked notes

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