Studies on the preparation and rearrangement of certain steroid oxides.

By preparative methods developed by Chakravorty and Wallis (1) and improved by Hicks, Berg, and Wallis (2) and by Alther and Reichstein (3) the 3(a)-hydroxycholenic acids containing double bonds at the C&& and the C1l-Clz positions respectively are readily available. An attractive method, therefore, for introducing oxygen either as a ketone or as a secondary hydroxyl at the Cn position lies in addition reactions of these unsaturated compounds. It would seem that one such method of introduction of this grouping essential in the synthesis of Compound E would consist in the rearrangement of oxides derived from the two cholenic acids mentioned above. Such reactions might be imagined to proceed according to the accompanying diagrams (I t,o XV). If instead of rearrangement simple hydrolysis of the oxido compounds should happen to occur, rearrangement studies of t,he glycols so formed would be of interest, for in the case of the C&Cn oxide the only possible keto compound which could be produced would be the desired Cn ketone. Therefore, it seemed pert.inent to study methods for the direct conversion of these unsaturated cholenic acids to keto and glycol derivatives through the preparation and rearrangement of their oxides. In order for us to obtain starting material for rearrangement studies, methods of preparing II and IX from the corresponding cholenic acids were investigat.ed. The application of perbenzoic acid to the C&-C, double bond was shown by Chakravorty and Wallis’ to yield an oxide mixed with a certain amomlt of starting material. Since in their hands difficulties were encountered in obtaining this oxide in a pure state, a method was sought whereby a stronger oxidizing agent could be used. The action of potassium permsngnnate, lea,d tetrapropionate, osmium tetroxide, hydrogen peroxide, and perbenzoic acid under a variety of conditions was investigated, and preliminary to our study of the action of certain of these reagents on II and IX, conditions for oxide formation