Chemical Ionization of TNT and RDX with Trimethylsilyl Cation

Crellin, Kevin C.; Widmer, Mirjam; Beauchamp, J. L.

doi:10.1021/ac961003q

Cited by 29 publications

(22 citation statements)

References 49 publications

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“…On the other hand, nitrobenzene and the explosives 1,3,5‐trinitro‐1,3,5‐triazacyclohexane (RDX) and 2,4,6‐trinitrotoluene (TNT) all produced [M+73] + adducts in a FT‐ICR instrument. Nitrobenzene showed no fragmentation but RDX produced fragments by cleavage of the triazacyclohexane ring (Crellin et al, ).…”

Section: Inter‐molecular Reactions Of Siliconium Ionsmentioning

confidence: 99%

Mass Spectrometric Fragmentation of Trimethylsilyl and Related Alkylsilyl Derivatives

Harvey

Vouros

2019

Mass Spectrometry Reviews

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This review describes the mass spectral fragmentation of trimethylsilyl (TMS) and related alkylsilyl derivatives used for preparing samples for analysis, mainly by combined gas chromatography and mass spectrometry (GC/MS). The review is divided into three sections. The first section is concerned with the TMS derivatives themselves and describes fragmentation of derivatized alcohols, thiols, amines, ketones, carboxylic acids and bifunctional compounds such as hydroxy‐ and amino‐acids, halo acids and hydroxy ethers. More complex compounds such as glycerides, sphingolipids, carbohydrates, organic phosphates, phosphonates, steroids, vitamin D, cannabinoids, and prostaglandins are discussed next. The second section describes intermolecular reactions of siliconium ions such as the TMS cation and the third section discusses other alkylsilyl derivatives. Among these latter compounds are di‐ and trialkyl‐silyl derivatives, various substituted‐alkyldimethylsilyl derivatives such as the tert‐butyldimethylsilyl ethers, cyclic silyl derivatives, alkoxysilyl derivatives, and 3‐pyridylmethyldimethylsilyl esters used for double bond location in fatty acid spectra. © 2019 Wiley Periodicals, Inc. Mass Spec Rev 0000:1–107, 2019

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Section: Inter‐molecular Reactions Of Siliconium Ionsmentioning

confidence: 99%

Mass Spectrometric Fragmentation of Trimethylsilyl and Related Alkylsilyl Derivatives

Harvey

Vouros

2019

Mass Spectrometry Reviews

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“…Explosives have been characterized by a number of spectroscopic techniques, such as middle-FTIR, Raman, UV/visible spectroscopy, GC-MS, etc. [6][7][8][9][10] However, they have not been completely characterized in the THz frequency range. In this paper, we present a spectroscopic characterization on explosives between 5 cm -1 and 650 cm -1 , and observe numerous new absorption lines in this range.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic characterization of explosives in the far-infrared region

Chen

Deng

et al. 2004

SPIE Proceedings

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Far infrared spectra of 14 commonly used explosive samples have been measured by using Fourier Transform Infrared Spectroscopy (FTIR) and THz Time-Domain Spectroscopy (THz TDS). New absorption resonances between 20 cm -1 and 650 cm -1 are reported. Below 20 cm -1 , no clear absorption resonances are observed in all the explosives. There is a good consistency of far-IR spectrum measured by Far-FTIR and by THz TDS in explosives 3,5-DNA and 2,4-DNT. Observed far-IR spectrum of TNT is compared with a previously reported theoretical calculation.

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“…The high specificity provided by ion/molecule reactions can be used to increase the selectivity of mass spectrometry in detection and identification of particular compounds in complex mixtures. Employing chemical reactions for unambiguous mass spectrometric detection of explosives has proved to be a useful approach, especially in chemical ionization experiments with selected reagent ions 1. In solution, it has long been known that electron‐deficient aromatic compounds can form anionic σ ‐adducts—Meisenheimer complexes—with various nucleophiles and these are important intermediates in a variety of aromatic reactions 2, 3.…”

mentioning

confidence: 99%

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

Song

Chen

Cooks

2005

Rapid Comm Mass Spectrometry

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Nucleophilic attack by the acetonyl anion (CH 3 COCH 2 À ) on highly electron-deficient nitroaromatics such as trinitrotoluene (TNT) results in the carbon-bonded anionic r-complexes (Meisenheimer complexes Acetone is a common reagent in ion/molecule reactions.7-15 Its reactivity with electron-deficient aromatic compounds has been studied using electrospray ionization (ESI) by doping acetone and a strong base (e.g. MeOK) into the spray solution. 6 The resulting deprotonated acetone acts as a nucleophile and attacks the aromatic ring to form a Meisenheimer complex. In another approach, also using ESI, acetone was doped into the curtain gas to react with dinitrophenide and trinitrophenide anions generated from dinitrobenzoic and trinitrobenzoic acid anions by CO 2 loss. 5These phenide anions first formed ion-neutral complexes with acetone followed by proton transfer from acetone to the phenide ring. The resulting acetonyl anion then forms a Meisenheimer complex with the electron-deficient aromatic compounds. Atmospheric pressure chemical ionization (APCI) is a sensitive and selective ionization technique which has found a wide range of applications. Compared to normal chemical ionization under reduced pressure, APCI has characteristic advantages for the implementation of ion/molecule reactions owing to its applicability to solution-phase nonvolatile compounds. [16][17][18][19] In this study, the reactivity of acetone with nitroaromatics and related compounds was investigated using APCI mass spectrometry. Deprotonated acetone (CH 3 COCH 2 À ) was generated by APCI and reacted with neutral nitroaromatics through nucleophilic attack on the electron-deficient benzene ring. This nucleophilic attack leads to the formation of the carbon-bonded anionic s-complex (Meisenheimer complex), which dissociates via distinctive HNO 2 and CH 3 COCH 3 /CH 2 COCH 3 elimination routes.

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Chemical Ionization of TNT and RDX with Trimethylsilyl Cation

Cited by 29 publications

References 49 publications

Mass Spectrometric Fragmentation of Trimethylsilyl and Related Alkylsilyl Derivatives

Mass Spectrometric Fragmentation of Trimethylsilyl and Related Alkylsilyl Derivatives

Spectroscopic characterization of explosives in the far-infrared region

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

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