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Gas‐phase fragmentation of γ‐lactone derivatives by electrospray ionization tandem mass spectrometry
Author(s) -
Crotti Antonio E. M.,
BronzeUhle Erika S.,
Nascimento Paulo G. B. D.,
Donate Paulo M.,
Galembeck Sérgio E.,
Vessecchi Ricardo,
Lopes Norberto P.
Publication year - 2009
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.1682
Subject(s) - chemistry , fragmentation (computing) , tandem mass spectrometry , ketene , collision induced dissociation , electrospray ionization , protonation , mass spectrometry , hydroxymethyl , dissociation (chemistry) , electrospray , computational chemistry , medicinal chemistry , analytical chemistry (journal) , ion , stereochemistry , organic chemistry , chromatography , computer science , operating system
Fragmentation reactions of β‐hydroxymethyl‐, β‐acetoxymethyl‐ and β‐benzyloxymethyl‐butenolides and the corresponding γ‐butyrolactones were investigated by electrospray ionization tandem mass spectrometry (ESI‐MS/MS) using collision‐induced dissociation (CID). This study revealed that loss of H 2 O [M + H −18] + is the main fragmentation process for β‐hydroxymethylbutenolide (1) and β‐hydroxymethyl‐γ‐butyrolactone (2). Loss of ketene ([M + H −42] + ) is the major fragmentation process for protonated β‐acetoxymethyl‐γ‐butyrolactone (4), but not for β‐acetoxymethylbutenolide (3). The benzyl cation ( m / z 91) is the major ion in the ESI‐MS/MS spectra of β‐benzyloxymethylbutenolide (5) and β‐benzyloxymethyl‐γ‐butyrolactone (6). The different side chain at the β‐position and the double bond presence afforded some product ions that can be important for the structural identification of each compound. The energetic aspects involved in the protonation and gas‐phase fragmentation processes were interpreted on the basis of thermochemical data obtained by computational quantum chemistry. Copyright © 2009 John Wiley & Sons, Ltd.