Reaction #93005

ord-51711f58cf9043d294756a7ccce7d9b7

Reaction equation

CCCCCCC(=O)O
n-heptanoic acid
[Na+].[OH-]
NaOH
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
CN(C)C=O
DMF
→
CCCCCCC(=O)OCC(=O)O[C@H]1[C@@H](CC)C[C@H]2[C@@H]3CCC4=CC(=O)CC[C@@H]4[C@H]3CC[C@@]21C
above-identified compound
Yield 64.0%
CCCCCCC(=O)OCC(=O)O[C@H]1[C@@H](CC)C[C@H]2[C@@H]3CCC4=CC(=O)CC[C@@H]4[C@H]3CC[C@@]21C
16β-Ethyl-17β-n-heptanoyloxyacetoxy-4-estren-3-one
Yield 64.0%

Reactants

CCCCCCC(=O)O
n-heptanoic acid
[Na+].[OH-]
NaOH
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
CN(C)C=O
DMF

Reagents

None

Solvents

CC(C)=O
acetone
O
water
CCOC(C)=O
ethyl acetate

Conditions

Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    workup.ADDITIONare serially added to the above solution
  2. 2
    TemperatureThe mixture is refluxed for 5 hours
  3. 3
    TemperatureAfter cooling
  4. 4
    Washthe mixture is washed with water and saturated aqueous sodium chloride solution
  5. 5
    Dryingdried over anhydrous magnesium sulfate
  6. 6
    workup.DISTILLATIONThe solvent is then distilled off under reduced pressure
  7. 7
    Wash400 ml of diisopropyl ether-n-hexane (2:3), elution
  8. 8
    workup.ADDITIONis carried out with 1000 ml of a 1:1 mixture of the same solvents
  9. 9
    OtherThe eluate is evaporated under reduced pressure
  10. 10
    Otherto remove the solvent

Procedure

In 30 ml of acetone is dissolved 2.6 g of n-heptanoic acid, and 10 ml of 2N-NaOH, 4.2 g of 16β-ethyl-17β-bromoacetoxy-4-estren-3-one, 30 ml of DMF and 10 ml of water are serially added to the above solution. The mixture is refluxed for 5 hours. After cooling, 400 ml of ethyl acetate is added and the mixture is washed with water and saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent is then distilled off under reduced pressure and the residue is subjected to column chromatography. Following 400 ml of diisopropyl ether-n-hexane (2:3), elution is carried out with 1000 ml of a 1:1 mixture of the same solvents. The eluate is evaporated under reduced pressure to remove the solvent, giving 3.0 g of the above-identified compound as a light-yellow viscous oil.

Source

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