STUDIES IN STEROID METABOLISM

Abstract

The isolation from human urine of Ag-etiocholenolone (III) (Fig. 1) and Ag-androstenolone (IV), both derived by dehydration of the adrenocortical metabolites 11-hydroxyetiocholanolone (I) and 11-hydroxyandrosterone (II), is described in this report.Since the presence of ll-hydroxyetiocholanolone has been established in a very high proportion of patients with neoplastic disease and is very rarely found in normal subjects (5-8), this investigation has a very significant bearing on cancer.The presence of this unusual steroid could easily have been overlooked, were it not for the systematic application of the powerful tool afforded by infra-red spectrometry.The investigation, therefore, is reported as an application of a methodical procedure to the elucidation of the chemical structure of the compounds.The more purely clinical aspects of the problem have been published elsewhere (5-8).Infra-red spectrometry permits the positive identification of a compound by comparison of the spectrum with that of a known, pure substance (9, 10).For this purpose, it is not necessary that the substance be obtained in crystalline form, since, indeed, non-crystalline eluates from a chromatogram often show spectra identical with those obtaiqed from authentic samples.Prior to the use of infra-red spectrometry, it was necessary to depend upon the more usual criteria of identity, such as the constancy of properties after repeated chromatography, melting point of a pure sample and of mixtures, rotation, and the like, together with the preparation of suitable derivatives.By these means we, as well as others, have isolated and characterized a number of urinary steroids, including androsterone and etiocholanolone, two of the more abundant ketosteroids.