In an earlier publication (1) a procedure was described for the preparation of certain steroids which are substituted at carbon atom 6 by an acetoxyl group. The arrangement in ring A of these compounds was the same as in the most active hormones of the androstane and pregnane series. Hence carbon atom 3 existed as carbonyl carbon and there was a double bond between carbon atoms 4 and 5. The examples given were the preparation of 6(a)-acetoxyandrostenedione and of 6(a)-acetoxydesoxycorticosterone. It was pointed out that 6(a) -acetoxyprogesterone (VI) previously obtained by Ehrenstein and Stevens (2) according to another procedure should also be accessible by means of the new scheme. The present investigation demonstrates that this is actually the case and that the new method is preferable to the old one.Starting material for this sequence of reactions was 5-pregnene-20-one-3(/3)-ol (I). Treatment of this substance with perbenzoic acid yielded mainly (65%) the (5,6)(a)-oxide (II) as was shown by the subsequent reactions. It was pointed out in the earlier paper (1) that (5,6) (a)-oxides furnish with glacial acetic acid 6-acetoxy compounds, whereas (5,6)(dioxides yield 5-acetoxy compounds. When pregnane-(5,6)(a)-oxide-20one-3(/3)-ol (II) was treated with glacial acetic acid under proper experimental conditions, only a small quantity of the by-product, pregnane-20one-3(j3), 5,6(¿rans)-triol 3,6-diacetate (IV), resulted. The main product (61.3%) of the reaction was pregnane-2O-one-3(0) ,5,6(trans)-triol 6monoacetate (III). Acetylation of this compound with acetic anhydride yielded the above mentioned 3,6-diacetate (IV).We had previously prepared (2) the 6-monoacetate (III) by partial hydrolysis of the 3,6-diacetate (IV). For the 6-monoacetate (III) the melting point 222-226°was observed. The melting point of the same compound obtained by acetolysis of the (5,6)(a)-oxide (II), however, was 1 Aided by a grant from the Smith, Kline, and French Laboratories in Philadelphia.Read before the Division of Organic Chemistry at the St. Louis meeting of the

As was pointed out in a previous paper (1), progesterone is the only naturally occurring compound with pronounced progestational activity. It manifests a slight "cortin" action, in that large doses are capable of maintaining the life of adrenalectomized animals (2). Desoxycorticosterone (21-hydroxyprogesterone), which was synthesized (3) previous to its isolation from the adrenal cortex (4), appears to be the simplest type of chemical compound having adrenal cortical activity. It also has a progestational effect about one-tenth that of progesterone (5). After the discovery of desoxycorticosterone, it was anticipated that this substance would alleviate equally well all the different physiological manifestations of adrenal insufficiency. More recent investigations have shown, however, that although desoxycorticosterone is highly satisfactory in maintaining the life of adrenalectomized animals, it is less effective than the other adrenal cortical hormones when, for example, the aggravation of diabetes (6) or the prevention of muscle fatigue (7) is measured. These other hormones are derivatives of desoxycorticosterone which are oxygenated at carbon atoms 11 or 17, or both.

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