AbstractSome new compounds, including 3α, 16α‐dihydroxy‐pregnan‐20‐one (I) and 3α, 16α‐dihydroxy‐allopregnan‐20‐one (III), have been isolated from urine of patients with clinically compensated adrenogenital salt‐losing syndrome. Compound I seems to be responsible for the original salt loss. This effect could be demonstrated under certain conditions in male adrenalectomized rats. Compound III was also isolated from hog adrenals. The synthesis of these steroids and of a few others, stereoisomeric in positions 3, 5 and 16, and of a 5,6‐dehydro analog is described. There is some preliminary evidence for the presence of compound I and III in urines of origin other than patients with