Abstract
Epoxidation of 17,17-ethylenedioxy-3-methoxyoestra-1,3,5(10),9(11)-tetraene( 5) by a two-phase
procedure gave the labile 9α,11α-epoxide (11), treatment of which with lithium perchlorate in benzene
gave 17,17-ethylenedioxy-3-methoxy-97#946;-oestra-1,3,5(10)-trien-11-one (7). Deuteration of this by
prolonged treatment with the monosodium salt of (O,O'-2H2)hydroquinone in dry (O-2H)methanol
gave mainly the 98,12,12-trideutero ketone (24) (92% 2H3). Reduction of this with lithium aluminium
deuteride to a mixture of the 11-epimeric alcohols (27a) followed by dehydration gave 17,17-ethylenedioxy-
3-methoxy(l1,12,12-2H3)oestra-1,3,5(10),9(11)-tetraene (26) which upon reduction with
lithium/ammonia gave 17,17-ethylenedioxy-3-methoxy(11ζ,12,12-2H3)oestra-1,3,5(10)-triene (25).
Hydrolysis and demethylation of (25) followed by treatment with potassium acetylide in liquid
ammonia yielded 3,17-dihydroxy-19-nor-17a-(11ζ, 12, 12-2H3)pregna-1 ,3,5(10)-trien-20-yne (29) (2H4,
9.2; 2H3, 84.1; 2H3, 3.1; 2H1, 2.2; 2H0, 1.3%).
Reduction of the trideutero 9(11)-ene (26) with hexadeuterodiborane followed by treatment
with alkaline hydrogen peroxide afforded 17,17-ethylenedioxy-3-methoxy(9α,11β,12,12-2H4)oestra-
1,3,5(10)-trien-11α-ol (30a). Reduction of the corresponding tosylate (30b) with lithium aluminium
deuteride, then hydrolysis, demethylation and ethynylation gave 3,17-dihydroxy-19-nor-17α-
(9,l 1,11,12,12-2H5)pregna-1,3,5(10)-trien-20-yne (35) (2H5, 84.5; 2H4, 8.5; 2H3, 4.4; 2H2,
0.9; 2H1, 0.8; 2H0, 0.9%).