Synthesis of steroid compounds and related substances Communication 38. Analogs of doisynolic acid not containing a B ring

Summary

• 1. Reaction between the hydrochloride of 3-dimethylamino-4'-methoxypropiophenone (IV) and 1, 3-cyclohexanedione in presence of alkali gave the bicyclic triketone (V), which was converted into the corresponding enol acetate (VII) when boiled with acetic anhydride in presence of sodium acetate.

• 2. It was shown that 2-p-methoxyphenyl-1, 3-butadiene (X) readily undergoes diene condensation with maleic anhydride and with methyl methacrylate with formation of the normal adducts (XI) and (XIII). It was found that in these reactions it-is possible to use 2-p-methoxyphenyl-3-buten-2-o1 directly, as it is readily dehydrated under the conditions of the experiment.

• 3. Reaction between p-methoxyphenylmagnesium bromide and methyl 1-methyl-4-oxo-l-cyclohexanecarboxylate (XX) gave a mixture of 4-p-methoxyphenyl-1-methyl-3-cyclohexene-1-carboxylic acid (XIV), and the corresponding ester (XIII), the products being identical with those obtained previously by diene condensation of 2-p-methoxyphenyl-1, 3-butadiene (X) with methyl methacrylate.

• 4. Demethylation of 4-p-methoxyphenyl-1-methyl-3-cyclohexene-l-carboxylic acid (XIV) by the aid of aluminum chloride in boiling xylene gave the bicyclic phenol (XV), which is of interest for tests on estrogenic activity.