Investigation of the Impurities in Erythritol Tetranitrate (ETN) Using UHPLC‐QTOF

Abstract

In order to further gain a comprehensive chemical understanding of erythritol tetranitrate (ETN), the synthesis impurities of ETN were investigated using ultrahigh performance liquid chromatography with tandem high resolution mass spectrometry (UHPLC‐MS/MS). A total of 12 impurities were identified relating to the synthesis of ETN. We have synthesized pure analytical standards of erythritol‐1,4‐dinitrate (1,4‐EDiN) and erythritol‐1,2,4‐trinitrate (1,2,4‐ETriN). These isomerically pure standards have allowed for confirmation of the identity of some of the discovered impurities. Additionally, partially nitrated with sulfate substituted erythritol was identified which is theorized to have formed from the incomplete displacement of the formed sulfate group on the alcohol position during nitration.

Interpol review of the analysis and detection of explosives and explosives residues

“…Freye, C., Nguyen, T., and Tappan, B. used UHPLC-MS/MS to explore the synthesis impurities due to the manufacturing process of ETN. They found 12 such impurities and were able to analyze for them [ 328 ].…”

Chemical Evaluation and Performance Characterization of Pentaerythritol Tetranitrate (PETN) under Melt Conditions

“…The resulting amorphous solid was then purified by column chromatography using 20% EtOAc in hexane gradient affording PETriNal as an amorphous solid in 39% yield (362 mg, 1.34 mmol). 1 H NMR (400 MHz, CD 3 CN) δ (ppm) = 9.67 (s, 1H), 4.83 (s, 6H). 13…”

“…Although UHPLC-QTOF reliably identifies trace materials, quantification of those impurities can be challenging due to the requirement of pure analytical standards. 1 H NMR spectroscopy allows for a rough quantification of some of the dominant decomposition products in solution, assuming that the impurity is dissolved in the solvent, has protons, and has a peak in the spectrum that is distinct from the dominant PETN peak. The 1 H NMR spectrum of the unheated PETN in acetonitrile shows a single peak at 4.65 ppm (4 CH 2 ).…”

“…Explosives with nitrate ester groups are commonly used in commercial, medicinal, and synthetic chemistry applications and have been studied extensively for their properties. Recently, our lab and others have explored the chemical characteristics, thermal stability, and melting point behavior of a variety of nitrate esters, such as pentaerythritol tetranitrate (PETN), erythritol tetranitrate (ETN), and mannitol hexanitrate (MHN). − PETN has been shown to melt at 141 °C, followed by an onset of decomposition of the explosive at approximately 160 °C. Due to the close proximity of the melt and the decomposition onset, few studies have been conducted on PETN in the molten state.…”

Development of a Gas Chromatography with High-Resolution Time-of-Flight Mass Spectrometry Methodology for BDNPA/F

“…Analysis of thermally labile compounds such as explosives and energetic materials is often performed using liquid chromatography (LC) as opposed to gas chromatography (GC) to avoid any undesirable thermal decomposition in the inlet or analytical column. − This is especially true when evaluating decomposition products formed through thermal aging of energetic materials. ,, However, a drawback of LC is the difficulty in analyzing small molecules with higher volatilities and the lower separation efficiency compared to GC. While LC still appears to be the main choice of technique for the analysis of energetics, the use of GC has been becoming more significant since the introduction of programmed temperature vaporization (PTV) inlets. − One of the first studies for analyzing energetic materials by GC-MS using a temperature-programmable inlet was performed in 1996 by Yinon who was able to analyze thermally labile energetic samples without compound degradation in the inlet .…”