Novel cardenolides and derivatives

Cpds. (I) X = H, Cl or Br and St = an estrone or androstane residue, linked via C17, and pref. chosen from II-V. R' = H, (1-4C) alkyl, (5-6C) cycloalkyl, or acyl R2 = or =O R3 = H or Me R4 = or =O R5 = or =O R6 = H, lower alkanoyl or a hexoside or hexosyl residue Y = H, OH, or lower alkanoyloxy Z = H or OH Cardiotonics, anti-inflammatories, hypocholesterolemics, and mineralocorticoids. N-Bromosuccinimide (5.05 g.), was added portionwise to a soln. of 17-(3'-furyl)-3-methoxy-estra-1,3,5(10)-triene-17-ol(5.0 g.; prepd. as in US.3,271,392), in dioxan (250 ml.) and H2O (20 ml), stirred 30 mins., dild. (H2O), and extra. (Et2O). The extract was washed (NaHCO3 soln. and H2O), dried, and evapd., giving the 2-subst. 4-bromo-4-hydroxy-2-butenic acid lactone contng. some 4-hydroxy-2-butenic acid lactone. This (67 g.) in HOAc (335 ml.), was stirred 1 h. at 20 deg. with Zn (33.5 g.), filtered, dild. with H2O (3 l.), filtered, and chromat. on SiO2, eluting with PhH-Et2O, and recrystallizing from CH2Cl2-MeOH, giving I(X=H), m.p.172-4 deg.