Isopropenyl acetate → 1,17-Diacetoxy-3-methoxyestra-1,3,5(10),16-tetraene

HRID 839752Notes

Reaction equation

HRID 839752 reaction equation
[C:1]([O:4][C:5]1[C:22]2[C@@H:21]3[C@H:12]([C@H:13]4[C@@:17]([CH2:19][CH2:20]3)([CH3:18])[C:16](=[O:23])[CH2:15][CH2:14]4)[CH2:11][CH2:10][C:9]=2[CH:8]=[C:7]([O:24][CH3:25])[CH:6]=1)(=[O:3])[CH3:2].[C:26](OC(C)=C)(=[O:28])[CH3:27].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>>[C:1]([O:4][C:5]1[C:22]2[C@@H:21]3[C@H:12]([C@H:13]4[C@@:17]([CH2:19][CH2:20]3)([CH3:18])[C:16]([O:23][C:26](=[O:28])[CH3:27])=[CH:15][CH2:14]4)[CH2:11][CH2:10][C:9]=2[CH:8]=[C:7]([O:24][CH3:25])[CH:6]=1)(=[O:3])[CH3:2]

Participants

4

Reactant 3

HCID 7916Isopropenyl acetateHCID 521998p-Toluenesulfonic acid monohydrateHCID 544622991-Acetoxy-3-methoxyestra-1,3,5(10)-trien-17-one

Product 1

HCID 545479651,17-Diacetoxy-3-methoxyestra-1,3,5(10),16-tetraene

Procedure

A solution of 1-acetoxy-3-methoxyestra-1,3,5(10)-trien-17-one (8.84 g, 26 mM), isopropenyl acetate (132 g, 1320 mM) and p-toluenesulfonic acid monohydrate (1.34 g, 7 mM) is heated at 120° in a distilling flask equipped with a 5 inch Vigreaux column to insure slow distillation. After heating at 120° for 16 hrs, 5 ml of distillate is collected. The temperature is increased to 140° and after 45 mins an additional 60 ml of isopropenyl acetate is collected. The residue is poured into 750 ml of ether and the ether solution is extracted with saturated NaHCO3 solution and H2O. The ether extract is dried over MgSO4 and evaporated in vacuo to give a residue containing the enol acetate and recovered starting material as the major components. The residue is chromatographed on 300 g of neutral silica gel and the column is eluted with 0.5% acetone:petroleum ether to give 1,17-diacetoxy-3 -methoxyestra-1,3,5(10),16-tetraene, yield 6.1 g (61%); m.p. 118° (petroleum ether).

Workup

  1. customequipped with a 5 inch Vigreaux column
  2. distillationdistillation
  3. temperatureAfter heating at 120° for 16 hrs
  4. distillation5 ml of distillate is collected
  5. temperatureThe temperature is increased to 140° and after 45 mins an additional 60 ml of isopropenyl acetate
  6. customis collected
  7. additionThe residue is poured into 750 ml of ether
  8. extractionthe ether solution is extracted with saturated NaHCO3 solution and H2O
  9. extractionThe ether extract
  10. dry with materialis dried over MgSO4
  11. customevaporated in vacuo
  12. customto give a residue
  13. customrecovered
  14. customThe residue is chromatographed on 300 g of neutral silica gel
  15. washthe column is eluted with 0.5% acetone

Sources & evidence

ORD record
ord-311258b4d8b04c22ae5ff05f3a7ec3ae
Source dataset
uspto-grants-1978_06
Patent number
US04096253

Reaction notes

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