Journal article
Structure of olefin-imidacloprid and gas-phase fragmentation chemistry of its protonated form
R Fusetto, JM White, CA Hutton, RAJ O'Hair
Organic and Biomolecular Chemistry | ROYAL SOC CHEMISTRY | Published : 2016
DOI: 10.1039/c5ob02371h
Abstract
One of the major insect metabolites of the widely used neonicotinoid insecticide imidacloprid, 1 (1-[(6-chloro-3-pyridinyl)methyl]-N-nitro-1H-imidazol-2-amine), is the olefin 2. To better understand how the structure of olefin 2 relates to the gas-phase fragmentation of its protonated form, 2H+, X-ray crystallography, tandem mass spectrometry experiments and DFT calculations were carried out. Olefin 2 was found to be in a tautomeric form where the proton is on the N(1) position of the imidazole ring and forms a hydrogen bond to one of the oxygen atoms of the coplanar nitroamine group. Under conditions of low-energy collision-induced dissociation (CID) in a linear ion trap, 2H+, formed via el..
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Awarded by Australian Research Council
Funding Acknowledgements
We thank the Australian Research Council for financial support via the ARC Centre of Excellence for Free Radical Chemistry and Biotechnology (CE0561607). Roberto Fusetto thanks The University of Melbourne for a postgraduate scholarship and Michael Leeming and Athanasios Zavras for their support with the DFT calculations. We thank Dr W. Alex Donald and Huixin Wang from the University of New South Wales for their help with the molecular dynamic simulations. For generously providing computational resources high-performance computing facilities, we thank the Victorian Partnership for Advanced Computing and the School of Chemistry at the University of Melbourne.