Molecular configuration and conformation of aldosterone, 18-hydroxy-11-deoxycorticosterone and a new urinary 18-hydroxy-steroid—an n.m.r. study

Abstract

The 1Hmr and 13Cmr spectra of aldosterone in various solvents show only the tautomeric forms with hemi-acetal[11–18] and hemi-ketal [18–20] bridges. The predominant form of 18-hydroxy-11-deoxycorticosterone (18-OH-DOC) in CDCl 3 (compound M of Dominguez) is the hemi-ketal [18–20] tautomer. Two forms are detected in CD 3OD: the hemiketal tautomer and very likely a dimer. Other derivatives are found in the presence of water and small amounts of acid. The 18-hydroxy-tautomer with a 2O-C O is not found. Two unknown steroids (compound x and compound y) were isolated from the urine of patients with hypertension and/or adrenal disorders. The 1Hmr spectroscopy indicates that the following structure can be proposed for compound x: a: a derivative of dihydro-18-hydroxy-deoxycorticosterone hydroxylated either at 4β and 9α or less probably at 5α and 9α. b: a derivative of dihydro-18-hydroxy-dehydrocorticosterone hydroxylated either at 4β or 5α or 9α. The behaviour of compound x in solution is very similar to that of 18-OH-DOC (predominance of the 18–20 hemi-ketal, formation of dimer and of other derivatives).