Stereospecific Ion—Molecule Reactions of Anabolic-Type Steroid Tertiary Alcohols with Proton-Donating Cations

Abstract

Isobutane and methane chemical ionization (CI) mass spectra of C-17a-epimeric, 17a-substituted 3-methoxyestra-1,3,5(10),8-tetraen-17a-ols and at C-17-epimeric 17-substituted 3-methoxyestra-1,3,5(10)-trien-17-ols, as well as of some their derivatives, have been studied. In each epimeric pair, the peak intensity ratio [MH–H₂O]⁺ / [MH]⁺ is greater for stereoisomers having an axial (or quasi-axial) hydroxyl group. The same regularity in the peak intensity ratio [MH–CH₃COOH]⁺ / [MH]⁺ is valid for acetates in the D-homo series. The observed quantitative differences in CI mass spectra of epimers are explained by steric hindrance of the attack of the proton-donating cation caused by the angular 18-methyl group. No differences in the ease of elimination of the silanol molecule were observed in CI mass spectra of epimeric silyl ethers.