Mass spectra of steroidal alkyl ethers—I

The mass spectral fragmentation of saturated and unsaturated steroidal methyl and ethyl ethers and ethers of 4,4‐dimethyl steroids are studied and compared to the fragmentation of steroidal alcohols, trimethylsilyl ethers and ethylene ketals. Unlike the trimethylsilyl ether the small fragment containing the alkoxy group is neither the base peak nor a very strong peak in the spectrum. A significant peak occurs at [M — ROH] +· , however, sometimes even constituting the base peak of the spectrum. The fragmentations of the alkyl ethers are largely dependent on their environments. The present results also show the generalization that methyl ethers are better leaving groups than the corresponding alcohols in fragmentation processes, is not always valid.