The Structure and Function of Oestrogens. I. Synthesis of 4b-Methyl-trans-4b,5,6,10b,11,12-hexahydrochrysene-2,8-diol

Abstract

Oxidation of 2,8-dimethoxy-5,6,11,12-tetrahydrochrysene (17) with m-chloroperbenzoic acid gave 2,8-dimethoxy-4b,5,6,10b,ll,l2-hexahydro-4b,10b-epoxychrysene (20). Treatment of this with methylmagnesium bromide afforded an inseparable mixture of 2,8-dimethoxy-4b-methyl-4b,5,6,12- tetrahydrochrysene (28) and 2,8-dimethoxy-5,6-dihydrochrysene (18) in the ratio 7 : 3. Hydrogenation of this mixture over 10% palladium-charcoal gave 2,8-dimethoxy-4b-methyl-trans-4b,5,6,10b,11,12- hexahydrochrysene (30) which was readily separable from (18). Demethylation of compound (30) yielded 4b-methyl-trans-4b,5,6,10b,11,12-hexahydrochrysene-2,8-diol (11a), which was required for assay as an oestrogen.