The D-Homoannulation of 17α-Hydroxy-20-ketosteroids¹

Origin of Pregnanetriol in a Patient with Adrenal Carcinoma

“…This high specific activity was confirmed by the isolation of 3a,17a/3-dihydroxy-17aa-methyl-D-homoetiocholane-17-one, a rearrangement product of 17-hydroxypregnanolone when the latter is subjected to prolonged chromatography (17). The effluents from System A were rechromatographed in System D for 24 hours and afforded 2,060 cpm in 270 fxg of the D-homosteroid, as measured by the macro Zimmermann method (17).…”

“…The effluents from System A were rechromatographed in System D for 24 hours and afforded 2,060 cpm in 270 fxg of the D-homosteroid, as measured by the macro Zimmermann method (17). This represented a specific activity of 7,350 cpm per mg for 17-hydroxypregnanolone, from which it was derived.…”

“…T HE EXCRETION of pregnane-3a, 17,20a:-triol may be elevated with some types of adrenocortical hyperfunction, often accompanied by increased amounts of androsterone 1 and etiochoReceived February 23, 1962. This investigation was supported in part by a grant from the American Cancer Society and a research grant (CY-3207) from the National Cancer Institute of the National Institutes of Health, USPHS.…”

Studies of Acetylated Corticosteroids and Related 20-Oxopregnane Derivatives by Gas Liquid Chromatography

“…It is well known that 17 -hydroxy -20 -oxosteroids are susceptible to thermal rearrangement with the formation of n-homosteroids (8, 9) and the isomerization of 3a, 17a-dihydroxy-5/3-pregnan-20-one to 3a, 17a -dihydroxy -17ß -methyl -Dhomo-5/3-androstan-17aone has been reported to occur quantitatively during gas chromatography (19). In general, mixtures of products may be expected (9), and subsidiary peaks are observed for most of the ketols listed in Table III. The retention factor corresponding formally to 17a-hydroxylation (and rearrangement) is approximately 1.4. The 17 a-acetoxy-20-ketones (unsubstituted at C2i) appear to be stable to chromatography, giving well-defined single peaks: the retention factor for 17a-acetoxylation is 1.9.…”