反応 #456233

反応方程式

3-tetrahydropyranyloxy-estra-1,3,5(10),8-tetraen-17-one

difluoromethyldiphenylphosphine oxide

lithium diisopropylamide

→

17-difluoromethylene-3-tetrahydropyranyloxy-estra-1,3,5(10),8-tetraene

収率 60.8%

溶媒

ethyl acetate

water

tetrahydrofuran

tetrahydrofuran

反応条件

後処理

1. 1
   workup.STIRRINGstirred for 15 minutes
2. 2
   温度slowly heated at a bath temperature of from -50° C. to 100° C.
3. 3
   温度refluxed for 2.5 hours
4. 4
   洗浄washed with water
5. 5
   その他dried on sodium sulfate
6. 6
   濃縮concentrated by evaporation in a vacuum
7. 7
   その他chromatographed on silica gel with hexane/ethyl acetate

実験手順

A solution of 2.7 g of difluoromethyldiphenylphosphine oxide in 85 ml of tetrahydrofuran is slowly mixed with 5.3 ml of 2 M lithium diisopropylamide solution at a bath temperature of -50° C., and it is stirred for 1 hour. Then, a solution of 1.5 g of 3-tetrahydropyranyloxy-estra-1,3,5(10),8-tetraen-17-one in 42 ml of tetrahydrofuran is slowly added, stirred for 15 minutes, slowly heated at a bath temperature of from -50° C. to 100° C. and refluxed for 2.5 hours. For working-up, it is diluted with ethyl acetate and water, washed with water, dried on sodium sulfate, concentrated by evaporation in a vacuum and chromatographed on silica gel with hexane/ethyl acetate. 1.0 g of 17-difluoromethylene-3-tetrahydropyranyloxy-estra-1,3,5(10),8-tetraene is obtained as colorless crystals with a melting point of 124-125° C., [α]D22 =+2.0° (c =0.525% in pyridine).

出典