Abstract
The electron impact mass spectrum (70 eV) of 26-trimethylsilyloxy-4-cholesten-3-one shows a base peak at m/e 196, attributable to combination of the trimethylsilyl group with a fragment of m/e 123 produced by cleavage across ring B. 18O labelling confirms that the fragment of m/e 196 contains the 3-oxygen atom, and 2H labelling indicates retention of the trimethylsilyl moiety. Similar ions are observed from other Δ4-3-ketones with sidechain trimethylsilyloxy groups: abundances depend on the site of substitution. The corresponding enol trimethylsilyl ethers are readily separable from the keto forms by gas-liquid chromatography, and afford mass spectra in which the molecular ions are abundant, while ions of m/e 196 are of only moderate intensity.
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