Negative chemical ionisation and collision induced fragmentations of deprotonated hydroperoxides

The mass spectra and the collisional induced dissociations (CID) of deproto nated hydroperoxides, generated by negative chemical ionisation (NCI) with methane as ionising reagent, have been examined. The chemical hat the base peak corresponds to the [[M-H)-O](-) ion for all the compounds studied with the exception of t-butyl hydroperoxide. The O2H- ion is present in the spe ctra of all of these compounds that do not possess a phenyl group. This stu dy provides detailed behaviour of deprotonated hydroperoxides, [M-H](-). Th e presence of the O2H- ion in the CID spectra of the deprotonated molecules produced by NCI with methane can be used as a fingerprint for hydroperoxid es in functional group identification. Copyright (C) 1999 John Wiley & Sons , Ltd.