Mass Spectrometry

Fragmentation - Ketones


The molecular ion peak is quite intense.

Fragmentation patterns mimic those of the aldehydes. a-cleavage in ketones favors the loss of the larger alkyl group as shown in figure 36.

Figure 36. a-cleavage.

Alpha cleavage.

McLafferty rearrangement can take place for ketones with at least 3 carbons (see figure 37).

Figure 37. McLafferty rearrangement of a ketone.

McLafferty rearrangement of a ketone.

For aromatic ketones, a-cleavage usually occurs, which is followed by loss of carbon monoxide as indicated in figure 38.

Figure 38. Aromatic ketone fragmentation.

Aromatic ketone fragmentation.

The complete mass spectrum for 2-pentanone is given in figure 39, which illustrates most of these points.

Figure 39. Mass spectrum for 2-pentanone.

Mass spectrum for 2-pentanone.


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