Structure elucidation of two isomeric steroids: photolytical and thermal reaction products from norethisterone studied by two-dimensional nuclear magnetic resonance

Abstract

Two-dimensional nuclear magnetic resonance was used for the structure elucidation of two isomeric photoproducts of norethisterone, a commonly used progestogen in oral contraceptives. The predominant one of the two isolated products derived from photochemical decomposition of norethisterone upon irradiation with UV-B light (280-320 nm) was 5 alpha, 17 beta-dihydroxy-19-nor-17 alpha-pregn-20-yn-3-one. The minor photoproduct appeared to be the analogous 5 beta-isomer, i.e. 5 beta, 17 beta-dihydroxy-19-nor-17 alpha-pregn-20-yn-3-one. The latter compound was also obtained from the thermal reduction of norethisterone-4 beta, 5 beta-epoxide using aluminium amalgam in isopropanol. Two-dimensional NMR appeared to be superior to mass and IR spectrometry in identifying the isomers.