GB842922A - Improvements in or relating to steroid compounds - Google Patents

Abstract

The invention comprises steroidal dihydroperoxides in which the dihydroperoxide group is in the 3- or 17- position or, in the case of a steroid free from an acyl group in the 21-position, the 20-position having the general formula <FORM:0842922/IV(b)/1> n being 1, 2 or 3, and R and R1 being molecule proportions of the steroid neighbouring the 3-, 17- or 21-position, esters of said dihydroperoxides having the general formula <FORM:0842922/IV(b)/2> wherein n R and R1 have the above significance and R11 is an alkyl aryl, aralkyl group or the residue of a polyacid of which one carboxy group is esterified with the hydroperoxide group such as an ester group derived from succinic acid and tetroxanes of said dihydroperoxides having the general formula <FORM:0842922/IV(b)/3> wherein n, R and R1 have the above significance, and processes for the preparation of steroidal dihydroperoxides by reacting keto-steroids having a keto group in the 3- or 17- position or, in the case of a steroid unacylated in the 21- position, the 20- position with hydrogen peroxide in an anhydrous solvent in the neighbourhood of umbient temperature, e.g., in the presence of a catalytic amount of concentrated hydrochloric acid, for the preparation of esters of steroidal dihydroperoxides by treating the said steroidal dihydroperoxides with an acylating agent in the neighbourhood of ambient temperature, and for the preparation of the above steroidal tetroxanes by reacting the said steroidal dihydroperoxides with a mixture of acetic acid and sulphuric acid in the neighbourhood of ambient temperature. The keto-steroid reactant may be of the pregnane, androstane or estrane series and may contain hydroxy groups which may be esterified or otherwise protected by easily cleavable protective groups, protected keto groups, such as enamines, acetals and mercaptals halogen atoms or double bonds. The ketosteroid reactant may contain two or three keto groups capable of being converted into dihydroperoxide groups so that the end product may be a mixture of two or more different steroidal dihydroperoxides which may be separated by fractional crystallization. In the examples the following compounds are prepared:-The 20-dihydroperoxide of 3 a -acetoxy-etiochloone -11, 20-dione, 3 a -acetoxy-pregnan-20-one, and 3 a -acetoxy -11 b -hydroxy-pregnan-20-one, the 17-dihydroperoxide of 3 a -acetoxy-etiochloone -11, 17-dione, estrone acetate and equiline acetate, the 3- and 20-dihydroperoxides of progesterone, the 3-dihydroperoxides of 21-acetoxy-pregnane -3, 11, 20-trione, desoxycorticosterone and testosterone, the diacetate of the dihydroperoxide of 3a -acetoxy-pregnane -11, 20-dione, and bis (3 a -acetoxy-pregnane-11-one)-20-tetroxane. The 17 - acetate of eliocholon - 17 - ol and of androstan - 17 - ol are prepared by treating the 20-dihyroperoxides of pregnan -20-one and allopregnan -20-one respectively with formic acid. In an example 3 a , 17b -diacetoxy-etiochloan-11one is prepared by treating the 20-dihydroperoxide of 3 a -acetoxy-pregnane -11, 20-dione with formic acid.