| 摘要 |
<p>The invention comprises (a) a process for preparing 3a b - methyl - 3b - (1 - hydroxy -ethyl)-benz[e] -indene derivatives, including hydrogenated derivatives thereof, by reaction of a 3-oxo-3a b -methyl-benz-[e]-indene derivative, in which any keto groups other than in the 3-position are protected, with ethylidene-triphenyl phosphorono, to form a 3-ethylidene benz-[e]-indene derivative, if desired splitting off any ketone-protecting groups present, reducing any such keto group to an hydroxy group and converting this into its C1- 7 alkyl or 2-tetrahydropyranyl ether, and treating the 3-ethylidene compound so obtained first with a source of hydroboron radicals <F/1> and then, at a pH greater than 7, with hydrogen peroxide, and (b) 3-ethylidene-intermediates of formula <F/2> wherein R1 is a hydrogen atom or a C1- 7 alkyl group and Z is a carbonyl group, a group <FORM:1123305/C2/1> wherein R3 is a C1- 7 alkylene group, or a group <F/4> wherein R2 is a hydrogen atom or a C1- 7 alkyl or 2-tetrahydropyranyl group. The 3b -hydroxy-ethyl side-chain may be oxidized to a 3b -acetyl side-chain. 3a b ,6(a or b )-dimethyl-3-oxo-7,7-ethylenedioxy-5a (a or b )-9ab -9ba -perhydro-benz-[e]-indenes are prepared by ketalization of the corresponding 7-oxo-3-hydroxy-compounds to form the 3-hydroxy-7,7-ethylenedioxy derivatives, followed by oxidation with chromium trioxide. 3a b ,6b - dimethyl - 3b - hydroxy - 7 - oxo - 5ab , 9ab ,9ba -perhydrobenz-[e]-indene is prepared by catalytic hydrogenation of the corresponding 5a,6-dehydro-compound. Progesterone and 20-hydroxy-3-oxo-D 4-9b ,10a -pregnane are prepared by condensation of the corresponding des-A-5-oxo-steroid with methyl vinyl ketone.</p> |
