Isolation and Characterization of WHydroxy-17-ketosteroids*

In the course of numerous metabolic studies with testosterone4-P in man, radioactivity was detected in chromatographic areas that contained compounds more polar than either 5oandrostane-3,17-diol or its 5p epimer. In many patients, the amount of this radioactivity was from 1 to 3% of the total administered; with some 8ubjeCt8, however, it represented as much as 10% of the dose. Two dihydroxy-17-ketosteroids have been isolated from these polar fractions, and the structures have been elucidated. 18-Hydroxyetiocholanolone’ was isolated from the urine of a patient with a metastatic arrhenoblastoma, as well as from the urine of patients given large amounts of testosterone and etiocholanolone. Its 5a! epimer, 18-hydroxyandrosterone, was isolated from urine following administration of androsterone. The patient with an arrhenoblastoma received a tracer dose of testosterone-4-C”. Chromatography of the neutral urinary steroid extract yielded a dihydroxyketone with approximately the same specific activity found for androsterone and etiocholanalone. The material crystallized readily, and the elementary analysis was consistent with the composition ClpHaoOl. The acetylated product lacked absorption in the hydroxyl-stretching region (3799 to 3599 cm-i); this was taken as evidence that the hydroxyl groups were readily acetylated. The same metabolite was obtained from another patient in approximately 3% yield after the administration of substantial amounts of etiocholanolone. The provisional conclusion drawn from this was that the product was a saturated steroid of the 5/Sandrostane series, probably with a 3a-hydroxyl group and a ketone at C-17. An absorption band at 1733 cm-1 (KBr) was consistent with the presence of a carbonyl group in the 5-membered ring. Absorption at 1497 cm-’ (Ccl4 solution; CaFz prism) in the acetylated