Process for preparing...

C - Chemistry – Metallurgy – 07 – J

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C07J 1/00 (2006.01) C07J 13/00 (2006.01) C07J 71/00 (2006.01)

Patent

CA 2260121

A process is disclosed for preparing 16.alpha.-hydroxy-estra-1,3,5(10)-triene derivatives having the general formula (I), in which R1 stands for a hydrogen atom, an alkyl group with maximum 4 carbon atoms, a benzyl group or an acyl group with maximum 8 carbon atoms; and X and Y represent together an oxo group or X stands for a hydroxyl group and Y for a hydrogen atom. This process is characterised in that an estra-1,3,5(10),16-tetraene derivative is converted by means of peracids into a 16.alpha.,17.alpha.-epoxide, which is split by means of mineral acids or converted by means of a reagent which supplies bromine cations into the corresponding 16.alpha.-bromine derivative, which is converted into the 16.beta.-bromine derivative. The bromine is replaced by an hydroxyl group and if required the thus obtained 16.alpha.-hydroxy- 1,3,5(10)triene-17-one derivative is reduced by means of sodium hydroboron in the presence of a strong aqueous buffer solution with a pH value from 5 to 6.5 into the corresponding 16.alpha.,17.beta.-trihydroxy-estra-1,3,5(10)-triene derivative.

L'invention concerne un procédé de préparation de dérivés de 16.alpha.-hydroxy-estra-1,3,5(10)-triène qui répondent à la formule générale (I), dans laquelle R¿1? désigne un atome d'hydrogène, un groupe alkyle avec au maximum 4 atomes de carbone, un groupe benzyle ou un groupe acyle avec au maximum 8 atomes de carbone; et X et Y symbolisent ensemble un groupe oxo ou X désigne un groupe hydroxyle et Y un atome d'hydrogène. Ce procédé se caractérise en ce que l'on convertit un dérivé d'estra-1,3,5(10),16-tétraène en 16.alpha.,17.alpha.-époxyde au moyen de peracides, on clive celui-ci au moyen d'acides minéraux ou on le convertit dans le dérivé correspondant de 16.alpha.-brome au moyen d'un réactif qui libère des cations de brome, puis on convertit celui-ci en un dérivé de 16.beta.-brome, on remplace le brome par un groupe hydroxyle et on réduit le cas échéant le dérivé de 16.alpha.-hydroxy-1,3,5(10)triène-17-one ainsi obtenu au moyen d'hydrure de bore de sodium en présence d'une forte solution tampon aqueuse d'une valeur de pH comprise entre 5 et 6,5, jusqu'à obtenir le dérivé correspondant de 16.alpha.,17.beta.-trihydroxy-estra-1,3,5(10)-triène.

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