Use of malonic acid derivatives for the construction of substituted side chains in the position 17β of steroids

Using the Knoevenagel reaction condensation products of 3β-acetoxyandrost-5-en-17-one with diethyl malonate, ethyl cyanoacetate and malononitrile were prepared which converted to derivatives of 3β-hydroxypregn-5-en-21-oic acid. Reductions and oxidations of the double bonds in the positions 5,6 and 17,20 and the stereochemistry at atoms C(17) and C(20) of some derivatives were also investigated. From derivatives of 23,24-dinorchola-5,17(20)-diene-21,22-diol compounds with a 1,3-dioxane ring in the side chain were prepared.