Abstract
In view of the current interest in the electron‐impact induced rearrangements of both trimethylsilyl derivatives and bifunctionalized cyclohexanes, the mass spectral properties of several alkoxycyclohexanol trimethylsilyl ethers and alkoxycyclohexyl trimethylsilanes have been investigated. Using deuterium labeling, the basic fragmentation modes incurred upon electron‐impact of ethanol trimethylsilyl ether were elucidated. The major peaks in the spectrum of this simple ether occur also in those of the title compounds, the latter fragments having been formed by interaction of the two functional groups. Thus the initial rearrangement ion of mass 103 (e) from electron bombardment of 4‐ethoxycyclohexanol trimethylsilyl ether and 2‐ethoxycyclohexyl trimethylsilane corresponds to the [M CH~3~] ion from ethanol trimethylsilyl ether. Its further fragmentation has been studied using high resolution and metastable ion measurements, and the scope of the interaction between the alkoxy and trimethylsilyl groups, when silicon is attached both to oxygen and to carbon, has been determined. In addition, the origin of every ‘characteristic’ fragment ion has been elucidated on the basis of each corresponding peak in the spectra of several derivatives labeled specifically with deuterium. Peaks derived from initial ionization of both functionalities in each compound have been observed, although the majority of ions in the spectra of both series seem to be directed by fragmentations associated with the trimethylsilyl ether moiety.