Gas‐phase Smiles Rearrangement of Sulfonylurea Herbicides in Electrospray Ionization Mass Spectrometry |
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Authors: | Jia Zhang Yunfeng Chai Wei Wang Wei Shang Yuanjiang Pan |
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Institution: | 1. Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310027, China;2. Laprode (Zhejiang) Analysis Co., Ltd, Hangzhou, Zhejiang 310052, China |
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Abstract: | In the negative ion mode of electrospray ionization tandem mass spectrometry (ESI‐MS/MS) of four sulfonylurea herbicides, Smiles rearrangements were observed in rimsulfuron and nicosulfuron. In the case of rimsulfuron, two competitive gas‐phase Smiles rearrangements initiated by nitrogen anion and oxygen anion respectively were witnessed. The ion‐neutral complex was proposed as the reactive intermediate in the course of this unimolecular dissociation reaction of the oxygen attack Smiles rearrangement route. The density functional theory (DFT) was carried out to elucidate the mechanism as well as to show the possible transition states and the intermediates. |
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Keywords: | sulfonylurea herbicides Smiles rearrangement ion‐neutral complex mass spectrometry |
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