A gas chromatographic method for the determination of urinary regnanetriol (5β-pregnane-3α,17α,20α-triol), pregnanetriolone (3α,17α,20α-trihydroxy-5β-pregnan-11-one) and pregnanetetrol (5β-pregnane-3α,11α,17α,20α-tetrol) was used in the study of 20 normal subjects and 9 patients with congenital adrenal hyperplasia. The method using single alumina column chromatography as a preliminary purification step was proved to be sensitive enough to measure as little as 10 μg of each of the steroids. Neither pregnanetriolone nor pregnanetetrol was detected in the urine of normal subjects, while these abnormal urinary steroids were found in all patients with congenital adrenal hyperplasia. In these patients, an increase in the ratio (pregnanetriolone + pregnanetetrol)/pregnanetriol was observed after dexamethasone treatment. This ratio decreased markedly following the administration of metyrapone (2-methyl-1,2-dipyridyl-1-propanone). It was also observed that the ratio pregnanetetrol/pregnanetriolone decreased following the metyrapone administration and increased with the dexamethasone treatment.

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