GB1228211A - - Google Patents

Abstract

1,228,211. #<SP>9</SP>(<SP>11</SP>)-Steroids. ROUSSELUCLAT. 19 March, 1968 [20 March, 1967], No. 13140/68. Heading C2U. The invention comprises (A) 13#-alkyl-5Ochydroxy - 10# - (optionally substituted hydrocarbyl) - 9(11) - dehydro - steroids, excluding compounds containing a substituent attached by a carbon-carbon bond to the 17#-position; (B) 3,3 - ethylenedioxy - 5# - estra - 1(10),9(11)- diene - 5,17# - diol (X); and (C) the preparation of 13#-alkyl-5-hydroxy-10-(optionally substituted hydrocarbyl)-9(11) -dehydro-steroids from 13# - alkyl - 5,10 - epoxy - 9(11) - dehydrosteroids (in which any ceto groups are protected) (XI) by reaction with an optionally substituted hydrocarbyl magnesium bromide, chloride or iodide. A 3-hydroxy product may subsequently be oxidized to the corresponding 3- one. A product having an oxo, ketalized oxo, hydroxylimino or alkoxyimino group in the 3- position may subsequently be treated with acid to yield the corresponding 4,9(11)-bisdehydro-3- one. Compound X is isolated as a by-product from the reaetion of 3,3-ethylenedioxy-5,10-epoxy-5#- estr-9(11)-en- 17#-ol benzoate with MeMgBr according to (C) above (Example (III). 10a - Pregna - 4,9(11 - diene - 3,20 - dione is prepared from 17# - hydroxy - 10α - androsta- 4,19(11) - dien - 3 - one by successive protection of the 3-oxo group, Oppenauer oxidation of the 17#-hydroxy group and a Wittig reaction (Example III). Compounds XI are prepared as described in Specification 1,228,212. The present Specification additionally discloses the preparation of 3,20 - bis{ethylenedioxy) - 5α,10α - epoxy - 19- norpregn - 9(11) - ene and the corresponding 5#,10# - epoxide from 19 - norpregna - 5(10),- 9(11) - diene - 3,20 - dione via 3,20 - bis(ethylenedioxy) - 19 - norpregna - 5(10),9/11)- diene.