The mass spectra of carboxylic acids—I: Fragmentation mechanisms in maleic and fumaric acids and related compounds

The mass spectra of maleic acid, maleic acid-2,3-d, fumaric acid and fumaric acid-2,3-d have been examined and fragmentation mechanisms are proposed for these compounds. The molecular ion of the cis-acid fragments via H atom transfer from one carboxyl group to the other followed by loss of CO₂. The trans acid does not fragment significantly by this route and the former effect may be characteristic of molecules containing two carboxyl groups cis-oriented to each other. This hypothesis was successfully tested by examining the mass spectra of citraconic, itaconic and phthalic acids. Itaconic and mesaconic acids show some of the fragmentation characteristics of fumaric acid.