A series of steroidal 3/3-hydroxy-''-7-ones and A3|5-7-ones were prepared as potential anti-cortisone agents. Biological evaluation showed 7-ketopregnenolone, 7-keto-21-acetoxypregnenolone 3-acetate and pregna-3,5-diene-7,20-dione to have a mild order of activity. The 3/3-hydroxy (or acetoxy)-A6-7-ones were prepared by oxidation in the allylic (C-7) position with either f-butyl chromate or sodium chromate. The A3'5-diene-7-ones were prepared by boiling the 3/3-acyloxy-A5-7ones one hour in glacial acetic acid with 0.5% (w./v.) of /j-toluenesulfonic acid.

Steroidal 3-Hydroxy-3,5-dien-7-onbs 6303 ethanol and benzene was added to incipient crystallization; yield 20 mg., m.p. 128-133°, 109-125°dec. on admixture with starting material, m.p. 130-136°on admixture with authentic IV, Rgltlc identical with that of authentic IV.2-Acetoxymethyl-3,4,5,6-tetra-0-acetyl-l-bromo-l-deoxyn-glucitol (mannitol?) (VI). (a) With Hydrogen Bromide in Acetic Acid.-To a solution of 2 g. of the epoxide acetate II in 3 ml. of acetic acid was added 3 ml. of acetic acid nearly saturated with hydrogen bromide. After 2 min. at room temperature, the solution was poured slowly into 40 ml. of a saturated aqueous sodium bicarbonate solution. Solid sodium bicarbonate was added in small portions until the solution was slightly basic to litmus. This mixture was extracted with three 10-ml. portions of chloroform, the combined extracts dried with sodium sulfate and the solvent removed under reduced pressure to yield a thin sirup. Solution in benzene followed by removal of the solvent under reduced pressure gave a sirup which crystallized spontaneously. Recrystallization was effected from etherpetroleum ether (b.p. 30-60°); yield 1.06 g., m.p. 91-98°. Two additional recrystallizations from ether-petroleum ether (b.p. 30-60°) gave pure material, m.p. 99-101°u nchanged on recrystallization from methanol, [a]24D +30.9°(c 3.9, CHCla); X-ray powder diffraction data: 11.2226 vw27,

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