1247-70-7

Treatment of enol acetates of 3β-acetoxyandrost-5-en-17-one and its 5α-reduced analog, 5α-androstan-17-one, and estrone acetate, 1-4, with Pb(OCOCH3)4 in acetic acid and acetic anhydride gave the previously unreported products, 16β-(acetoxy)acetoxy-17-ketones 8-10 and 12, in 9-15% yields along with the known major products, 16β-acetoxy-17-ketones 5-7 and 11. Similar treatment of the 16β-acetoxy-17-ketones with the lead reagent did not yield the corresponding (acetoxy)acetates. Reaction of the enol acetate 3 with Pb(OCOCD3)4 in CD3COOD yielded principally the labeled (acetoxy)acetate 10-d3, which had a CD3COOCH2COO moiety at C-16β. In contrast, when the deuterated enol acetate 3-d3, which was obtained by treatment of the 17-ketone 14 with (CD3CO)2O in the presence of LDA and which had a CD3COO moiety at C-17, was reacted with Pb(OCOCH3)4, the resulting product was the labeled compound 10-d2. This product had a CH3COOCD2COO function at C-16β. Based on these results, along with further isotope-labeling experiments, it seems likely that the (acetoxy)acetate is produced through a lead (IV) acetate-catalyzed migration of the 17-acetyl function of the enol acetate to the C-16β-position followed by attack of an acetoxy anion of the lead reagent. Copyright

New and pharmacologically useful 17-amino-16-hydroxy-steroids of the androstane and oestrane series are disclosed having the formula I: STR1 and pharmaceutically acceptable non-toxic acid addition salts thereof, wherein: R1 =H or hydrocarbyl of one to six carbon atoms (preferably lower alkyl, such as methyl); R2 =H or hydrocarbyl of one to six carbon atoms (preferably lower alkyl, such as methyl); R3 =a free, esterified or etherified hydroxyl group; ring A inclusive carbon atoms 6 and 9 has one of the following configurations: STR2 in which R4 =a free, esterified or etherified hydroxyl group; R5 =O or H(R7), wherein R7 is a free, esterified or etherified hydroxyl group; R6 =H or methyl; and the dotted lines represent an optional double bond in 4,5- or 5,6-position; as well as the enantiomers and racemates of these steroids. The novel compounds have antiarrhythmic properties.