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

Abstract

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.