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The urinary steroids afford a means for evaluation of the production of steroid hormones by the adrenal and gonads. Any alteration in either rate of type of hormone production by the glands resulting from specific disease or from hormonal therapy therefore must be manifest by qualitative or quantitative change in the excretion of steroid hormone metabolites. In order to delineate the composition of these metabolites in normal healthy subjects, the present investigation describing the a-ketosteroid excretion pattern was undertaken. MATERIALS AND METHODSTwenty normal males, ranging in age from 21 to 76, were studied. Of this number, eighteen were White and one was Negro; Subject D31 was a Nisei. Subjects C21 and M21 were normal males hospitalized at the Peter Bent Brigham Hospital, Boston, Massachusetts, for the purpose of studying some of the metabolic effects of oral Cortisone and intravenous ACTH; Subjects K31, R32, R63, C64, M65, and M72 were subjects of similar study at the Baltimore City Hospitals, Baltimore, Maryland. Only control periods of these eight subjects are reported here. The remainder of the subjects are, or were, employees of this Institute, working and in apparent good health. The details of urine collection and handling in this laboratory have been reported previously (1).

Vol. 75 0.86 g. (0.01 mole) of vinyl ether, 0.098 g. (0.001 mole) of potassium acetate and 0.5 ml. of glacial acetic acid (0.01 mole) dissolved in 100 ml. of 80% dioxane. The solutions were sealed in Cams tubes and heated on a steam-bath for 64.5 hours. Distillation of the contents of one of the tubes into a 25-ml. portion of 2,4-dinitrophenylhydrazine reagent yielded no precipitate even on standing. Dilution of this same solution with water did yield a small amount of precipitate (less than 0.1 g.) melting point 174-177°, mixed m.p. with isobutyraldehyde 2,4-dmitrophenylhydrazone, 175-180°. The contents of the second tube were distilled into freshly prepared Fehling solution. No precipitate developed.Rate Measurements.-The rate measurements in anhydrous acetic acid and in "80%" dioxane were carried out as in previous work.3•5 The "80%" dioxane was the same solvent described previously.3 Good first order kinetics were observed.

The application of the methods which are described in the previous paper to the determination of the intensities of C-0 stretching bands in steroids is illustrated. Correlations between band intensities and molecular structures have been established on the basis of measurements on 66 steroids. The integrated absorption intensities of different types of carbonyl g-roups vary by a factor of four but the intensity for a given type of carbonyl group is sensibly constant in different compounds. The ketone intensity does not vary appreciably with the position of the carbonyl group in the steroid nucleus, but is significantly different when the carbonyl group is in a side chain. Systematic changes in intensity are ohserved when the carbonyl group is conjugated or when a halogen atom is introduced at a vicinal methylene group. In the di-and polycar-bony1 compounds investigated the carbonyl intensities were found to be additive within the limits of experimental error. Such measurements permit the number of carbonyl groups in a compound to be determined even where the bands overlap completely, and have been applied to the elucidation of the structure of steroids isolated from natural sources. Integrated absorption intensities are found to give more satisfactory structural correlations than maximal molecular extinction coefficients.