Process for the manufacture of 6.beta.,7-methylene-3-oxo-...

C - Chemistry – Metallurgy – 07 – J

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260/21, 260/39,

C07J 1/00 (2006.01) C07J 21/00 (2006.01) C07J 51/00 (2006.01) C07J 53/00 (2006.01) C07J 63/00 (2006.01) C07J 71/00 (2006.01)

Patent

CA 1084904

Abstract of the Disclosure The invention provides a novel general process for the manufacture of 6.beta.,7-methylene-3-oxo-4-ene-steroids by successlvely a)reacting a 3?,5.beta.-dihydroxy-6-ene-steroid which is optionally etherified or esterified in the 3-position with a zinc/copper-methylene iodide reagent to introduce the 6.beta.,7-methylene bridge, b) liberating sn etherified or esterified 3-hydroxyl group if such a group is present, c) tresting the resultant 6.beta.,7-methylene-3?,5.beta.-dihydroxy- steroid with an oxidising agent to dehydrogenate the 3-hydroxyl group to the oxo group, and d) dehydrating the 6.beta.,7-methylene- 5.beta.-hydroxy-3-oxo-steroid to form the 4,5-double bond. The starting materials, which form a novel class of compounds, can be obtained by a novel process by converting a 5.beta.,6- oxido-3?-hydrox -steroid with a selenol, for example phenyl- selenol, to a 6.alpha.-alkyl- or arylseleno-3?,5.beta.-dihydroxy- steroid, oxidising this compound with a peroxidic reagent, - 1 - for example hydrogen peroxide, in a weakly acid medium to give the corresponding 6-selenonyl compound, and converting this compound, preferably by treatment with a base, preferably with 1,5-diazabicyclo[4,3,0]non-5-ene, to give the 3?,5.beta.- dihytroxy-6-ene-steroid. During the course of these reactions, the 3-hydroxyl group is preferably temporarily protected by esterification or etherification. - la -

275416

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