Reaction #56620

Reaction equation

3,7β-dihydroxy-2-iodo-estra-1,3,5(10)-trien-17-one

aluminum isopropylate

→

colorless crystals

Yield 63.0%

3-Hydroxy-2-iodo-estra-1,3,5(10)-triene-7,17-dione

Yield 63.0%

Solvents

toluene

cyclohexanone

toluene

Conditions

Workup

1. 1
   workup.DISTILLATIONIn the meantime, a portion of the reaction mixture was distilled off
2. 2
   workup.ADDITIONAfter complete addition of the aluminum isopropylate, it
3. 3
   Temperaturewas refluxed for still another 5 hours
4. 4
   TemperatureThen, the reaction solution was cooled
5. 5
   workup.ADDITIONdiluted with 80 ml of dichloromethane and 30 ml of potassium/sodium tartrate solution
6. 6
   Otherwas separated from the aqueous phase
7. 7
   ExtractionThe aqueous phase was finally extracted with dichloromethane (3×30 ml)
8. 8
   Washthe combined organic phases were washed with a saturated NaCl solution
9. 9
   Otherdried on sodium sulfate
10. 10
    Concentrationconcentrated by evaporation in a rotary evaporator

Procedure

A solution of 206 mg (0.5 mmol) of 3,7β-dihydroxy-2-iodo-estra-1,3,5(10)-trien-17-one 14 in 15 ml of toluene and 4 ml of cyclohexanone was heated to 140° C. (oil bath temperature), and a solution of 400 mg of aluminum isopropylate in 10 ml of toluene was added drop by drop. In the meantime, a portion of the reaction mixture was distilled off. After complete addition of the aluminum isopropylate, it was refluxed for still another 5 hours. Then, the reaction solution was cooled and diluted with 80 ml of dichloromethane and 30 ml of potassium/sodium tartrate solution, and the resulting mixture was first stirred vigorously for 30 minutes before the organic phase was separated from the aqueous phase. The aqueous phase was finally extracted with dichloromethane (3×30 ml), and the combined organic phases were washed with a saturated NaCl solution, dried on sodium sulfate and concentrated by evaporation in a rotary evaporator. Flash chromatography (cyclohexane/ethyl acetate) yielded 129 mg (63%) of colorless crystals.

Source