Research Article

Reactivity of acetonyl anion with nitroaromatics: an atmospheric pressure chemical ionization study

  1. Yishu Song,
  2. Hao Chen,
  3. R. Graham Cooks*

Article first published online: 1 NOV 2005

DOI: 10.1002/rcm.2206

Issue

Rapid Communications in Mass Spectrometry

Rapid Communications in Mass Spectrometry

Volume 19, Issue 23, pages 3493–3499, 15 December 2005

Additional Information

How to Cite

Song, Y., Chen, H. and Cooks, R. G. (2005), Reactivity of acetonyl anion with nitroaromatics: an atmospheric pressure chemical ionization study. Rapid Communications in Mass Spectrometry, 19: 3493–3499. doi: 10.1002/rcm.2206

Author Information

  1. Department of Chemistry, 560 Oval Drive, Purdue University, West Lafayette, IN 47907, USA

*Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA.

Publication History

  1. Issue published online: 1 NOV 2005
  2. Article first published online: 1 NOV 2005
  3. Manuscript Accepted: 15 SEP 2005
  4. Manuscript Revised: 14 SEP 2005
  5. Manuscript Received: 11 AUG 2005

Funded by

  • Crane NSWC/DTRA. Grant Number: W912HZ-04-2-0001

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Abstract

Nucleophilic attack by the acetonyl anion (CH3COCHmath image) on highly electron-deficient nitroaromatics such as trinitrotoluene (TNT) results in the carbon-bonded anionic σ-complexes (Meisenheimer complexes). The complexes are generated at atmospheric pressure with relatively low internal energy and do not dissociate under atmospheric pressure chemical ionization conditions, but can be dissociated upon collisional activation to produce characteristic nitrobenzyl-substituted acetonyl anions via elimination of HNO2. Further fragmentation produces deprotonated nitrotoluene anions through the loss of CH2CO, while loss of CH2COCH3 and CH3COCH3 yields nitroaromatic molecular anions and their H-loss counterparts. Hydrogen/deuterium (H/D) scrambling is observed in the fragmentation products of the [TNT · CD3COCD2]− complex to extents which vary for different fragmentation pathways. Selective Meisenheimer complex formation, together with its distinctive fragmentation pattern, supplies a highly discriminatory method for detection of TNT and related compounds. Copyright © 2005 John Wiley & Sons, Ltd.

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