| abstract |
d,1-zearaleneone and mono- and diethers thereof, compounds having anabolic, estrogenic and fertility control properties, are prepared by a total chemical synthesis. An aromatic ring component, a diether of 2-formyl-4,6-dihydroxy benzoic acid, is prepared by selective reduction of a diether of 3,5-dihydroxy phthalic anhydride; an aliphatic component, 2-loweralkoxy-6methyltetrahydropyran-2-butyl triphenyl phosphonium halide, is prepared via a sequence of reactions involving the condensation of 2-hydroxyhexanoic acid- delta - lactone with pent-4-enyl magnesium bromide, subsequent treatment with alcoholic acid to form 2-(pent-4-enyl)-2-loweralkoxy-6-methyl tetrahydropyran, which substance is in turn ozonized, reduced with alkali metal borohydride, reacted with an alkyl or aryl sulfonyl halide, and then with sodium bromide or iodide to afford 2-( delta halobutyl)-2-loweralkoxy-6-methyl tetrahydropyran, which latter substance is reacted with triaryl phosphine to afford the abovestated aliphatic component. The aromatic and aliphatic components are coupled and the resulting 1-(3,5-diether-6-carboxyphenyl)-10hydroxy-1-undecen-6-one ring-closed with trifluoroacetic anhydride to yield d,1-zearalenone diether, which is cleaved with boron tribromide or pyridine hydrochloride to d,1-zearaleneone. |