Phosphorus oxychloride → HCID 86738310, compound

Participants

Reaction Steps

A suspension of 1.0 g of sodium acetate in 30 ml of chloroform and 30 ml of methylal is combined with 1.9 ml of phosphorus oxychloride and refluxed for 1 hour. The reaction mixture is combined with 1.0 g of 17β-acetoxy-17α-ethynyl-4-androsten-3-one and, under reflux, 1.9 ml of phosphorus oxychloride is added dropwise within 2 hours. The mixture is refluxed for 1 hour, cooled, and rendered alkaline by the dropwise addition of saturated soda solution. The organic phase is separated and concentrated under vacuum. For working-up purposes, the crude product is mixed with a small amount of methylene chloride and water, as well as 5 g of soda. After steam distillation, the product is vacuum-filtered, the residue washed neutral with water, and purified on 105 g of silica gel with a hexane/ethyl acetate gradient (0-50% ethyl acetate). In this way, 630 mg of 17β-acetoxy-17α-ethynyl-6-methylene-4-androsten-3-one is isolated, mp 158°-160° C.

Provenance & Evidence