Synthesis of steroids and related compounds

Abstract

1. By the condensation of 1,3-cyclohexanedione (I) with 3-buten-2-one, a mixture of the 3-oxobutyl derivatives (II) and (III) was formed. By the action of diazomethane on the ketone (II), the pure methyl ether of the enol form of 2-(3-oxobutyl)-1,3-cyclohexanedione was obtained, and treatment of this with potassium tert-butoxide gave the bicyclic methoxy ketone(XI ). 2. Hydrolysis of the methoxy ketone (XI) with dilute hydrochloric acid gave 3,4,7,8-tetrahydro-1,6(2H, 5H)-naphthalenedione (IX) In high, yield. 3. With diazomethane 3,4,7,8-tetrahydro- 1,6(2H,5H)-naphthalenedione (IX) gave the bicyclic methoxy ketone (VI), which was converted by dehydrogenation with sulfur into the known 3,4-dihydro-6-methoxy-1(2H)-naphthalenone (VII). 4. By reaction of p-methoxyphenylmagnesium and 4-methoxyw-o-tolylmagnesium bromides with the methoxyketone (XI). and subsequent hydrolysis, isomerization, and dehydration of the reaction products, the dienic ketones (XIII) and (XIV) were obtained. These ketones are of interest as model steroid analogs not containing ring B.