Translational energy release and stereochemistry of steroids. XI—Determination of the configuration of α,β‐unsaturated 3‐keto steroid alcohols with the hydroxyl group in rings C and D

The elimination of water from metastable molecular ions of epimeric hydroxy steroids of the Δ4‐3‐keto series containing a hydroxyl group in the conformationally rigid rings C and D has been studied. The measurement of translational energy released during the loss of water and collision‐induced decomposition (CID) mass‐analysed ion kinetic energy (MIKE) spectrometry were the techniques used. It was found that it is possible to determine the configuration of the hydroxy steroids of this series on the basis of the CID MIKE spectra of [M − H2O]+˙ ions formed by dehydration of metastable molecular ions in the first field‐free region of a reversed geometry double‐focusing mass spectrometer.