ESI formation of a Meisenheimer complex from tetryl and its unusual dissociation |
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Authors: | Cécile Hubert Héloïse Dossmann Xavier Machuron‐Mandard Jean‐Claude Tabet |
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Institution: | 1. CEA, DAM, DIF, , F‐91297 Arpajon, France;2. Institut Parisien de Chimie Moléculaire (Chimie Structurale Organique et Biologique), Université Pierre et Marie Curie, , Place Jussieu, F‐75252 Paris Cedex 05, France |
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Abstract: | The reactivity of the explosive tetryl (N‐methyl‐N,2,4,6‐tetranitroaniline; Mw = 287 u) was studied using electrospray ionization in negative mode. The main species detected in the spectrum corresponds to the ion observed at m/z 318 (previously assumed to be the odd‐electron ion tetryl + HNO]‐?, C7H6O9N6). In this study, we show using D‐labeling combined with high‐resolution mass spectrometry that this species corresponds to an even‐electron anion (i.e. C8H8O9N5), resulting from the formation of a Meisenheimer complex between tetryl and the methanol used as the solvent. Fragmentation of this complex under CID conditions revealed an unexpected fragment: the formation of a 2,4,6‐trinitrophenoxide anion at m/z 228. 18O‐labeling combined with quantum chemical calculations helped us better understand the reaction pathways and mechanisms involved in the formation of this product ion. This occurs via a transition state leading to a SN2‐type reaction, consequently evolving toward an ion‐dipole complex. The latter finally dissociates into deprotonated picric acid. Copyright © 2013 John Wiley & Sons, Ltd. |
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Keywords: | Meisenheimer complex tetryl solvent effect DFT calculation ion‐dipole intermediate |
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