Bifunctional even-electron ions. V. Fragmentation behaviour of aliphatic hydroxonium ions containing an additional cyano group

✍ Scribed by U. I. Záhorszky; P. Schulze

• Publisher: John Wiley and Sons
• Year: 1989
• Tongue: English
• Weight: 710 KB
• Volume: 24
• Category: Article
• ISSN: 1076-5174
• DOI: 10.1002/oms.1210240908

✦ Synopsis

The fragmentation behaviour of a series of bifunctional hydroxonium ions C,H,-C(=OH)-(CH,),-CN

(n = 0-6), a,, has been investigated by electron impact mass spectrometry. The type of interaction-induced reactions depend strongly on the chain distance between the oxonium and the cyano moiety, but the initial step in all cases is proton transfer from the hydroxy to the cyano group. The following selective primary fragmentations have been found: loss of C=NH (HCN) from a@, loss of CH,=C=NH from a,, loss of HNCO from a2-u,, loss of CH,-CH-C=O from a,-u6, and loss of CO from a,. In addition, loss of NH, and H,O, respectively, are observed as general fragmentations, except for the lowest homologues (ao and a,). Mechanistic pathways of the selective reactions have been deduced with the aid of metastable ion spectra, high resolution, deuterium labelling and comparison of metastable ion spectra with those of independently generated ions.