In mass spectrometry, cycloalkanes exhibit distinct fragmentation patterns due to the inherent stability of their molecular ions compared to linear or branched alkanes. The ring structure of cycloalkanes provides additional stability to the molecular ions, often resulting in prominent ion peaks in the mass spectrum.

For example, cyclohexane molecular ions have a mass-to-charge ratio (m/z) of 84, which tends to produce a stronger signal than linear alkanes like hexane. This stability comes from the closed-ring structure, which stabilizes the ion. A common fragmentation pathway for cyclohexane involves the loss of an ethylene molecule (C₂H₄), leaving behind a radical cation with an m/z of 56. This resultant cation is highly stable and frequently forms the base peak, the most intense signal in the mass spectrum.

Figure 1. Fragmentation of the cyclohexane molecular ion.

Branched cycloalkanes, such as methyl cyclopentane, exhibit additional fragmentation pathways due to side chains. Alongside the typical ethylene loss, the molecular ion can also lose side chains, such as a methyl group (CH₃). For instance, the molecular ion may lose a methyl radical (CH₃), resulting in a cyclopentyl cation. This cyclopentyl cation further fragments, typically leading to the loss of ethylene, resulting in a stable propyl radical cation.

These fragmentation patterns demonstrate how ring structures and branching affect ion stability in the mass spectrometer. The characteristic loss of small molecules like ethylene and side chains produces highly stable cations, which are observed as prominent peaks in the spectrum.

Figure 2. Fragmentation of methyl cyclopentane into (top) ethene and a butyl radical cation; (bottom) a methyl radical and a cyclopentyl carbocation, followed by further fragmentation of the cyclopentyl carbocation.