Factors Influencing Triacetone Triperoxide (TATP) and Diacetone Diperoxide (DADP) Formation: Part 2

Oxley, Jimmie C.; Smith, James L.; Steinkamp, Lucus; Zhang, Guang

doi:10.1002/prep.201200215

Cited by 21 publications

(18 citation statements)

References 16 publications

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“…Although it is difficult to fully explain the observed shifts in the IRMS and GC‐IRMS data from the chemical reactions and associated isotope chemistry, this work does provide clear evidence to support the postulated reaction mechanism for the acid‐catalyzed synthesis of TATP from acetone and hydrogen peroxide . The established correlations or lack thereof between isotopic ratio values of TATP and its precursors given in Figs and are in agreement with the reaction mechanism depicted in Fig.…”

Section: Resultssupporting

confidence: 80%

“…Figure shows the postulated reaction mechanism of TATP formation from acetone and hydrogen peroxide. The selection criteria for acetone samples were based on the carbon and hydrogen isotopic compositions, as the reaction mechanism suggests that acetone is the donor of both carbon and hydrogen in the formation of TATP . For hydrogen peroxide, the selection criteria were based on the oxygen isotopic compositions, as hydrogen peroxide is suggested to be the donor of oxygen in the formation of TATP.…”

Section: Resultsmentioning

confidence: 99%

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The Potential of Isotope Ratio Mass Spectrometry (IRMS) and Gas Chromatography‐IRMS Analysis of Triacetone Triperoxide in Forensic Explosives Investigations

Bezemer

Koeberg

Heijden

et al. 2016

Journal of Forensic Sciences

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Studying links between triacetone triperoxide (TATP) samples from crime scenes and suspects can assist in criminal investigations. Isotope ratio mass spectrometry (IRMS) and gas chromatography (GC)-IRMS were used to measure the isotopic compositions of TATP and its precursors acetone and hydrogen peroxide. In total, 31 TATP samples were synthesized with different raw material combinations and reaction conditions. For carbon, a good differentiation and a linear relationship were observed for acetone-TATP combinations. The extent of negative (δ(13) C) fractionation depended on the reaction yield. Limited enrichment was observed for the hydrogen isotope (δ(2) H) values of the TATP samples probably due to a constant exchange of hydrogen atoms in aqueous solution. For oxygen (δ(18) O), the small isotopic range and excess of water in hydrogen peroxide resulted in poor differentiation. GC-IRMS and IRMS data were comparable except for one TATP sample prepared with high acid concentration demonstrating the potential of compound-specific isotope analysis. Carbon IRMS has practical use in forensic TATP investigations.

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Section: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 99%

The Potential of Isotope Ratio Mass Spectrometry (IRMS) and Gas Chromatography‐IRMS Analysis of Triacetone Triperoxide in Forensic Explosives Investigations

Bezemer

Koeberg

Heijden

et al. 2016

Journal of Forensic Sciences

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“…26 Caution : TATP and DADP are shock-, friction-, heat-, and spark-sensitive high explosives and can decompose violently in strong acid. 26−29 Peroxide 7 was prepared from the corresponding tertiary bromide following a reported procedure; 2b peroxide 8 was available through methylation of the known tertiary hydroperoxide. 30…”

Section: Results and Discussionmentioning

confidence: 99%

Reductive Cleavage of Organic Peroxides by Iron Salts and Thiols

et al. 2018

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Despite the low bond strength of the oxygen–oxygen bond, organic peroxides are often surprisingly resistant to cleavage by nucleophiles and reductants. As a result, achieving decomposition under mild conditions can be challenging. Herein, we explore the reactivity of a selection of peroxides toward thiolates, phenyl selenide, Fe(II) salts, and iron thiolates. Peroxides activated by conjugation, strain, or stereoelectronics are rapidly cleaved at room temperature by thiolate anions, phenylselenide, or Fe(II) salts. Under the same conditions, unhindered dialkyl peroxides are only marginally reactive; hindered peroxides, including triacetone triperoxide and diacetone diperoxide (DADP), are inert. In contrast, all but the most hindered of peroxides are rapidly (<1 min at concentrations down to ∼40 mM) cleaved by mixtures of thiols and iron salts. Our observations suggest the possible intermediacy of strongly reducing complexes that are readily regenerated in the presence of stoichiometric thiolate or hydride. In the case of DADP, an easily prepared explosive of significant societal concern, catalytic amounts of iron and thiol are capable of promoting rapid and complete disproportionation. The availability of inexpensive and readily available catalysts for the mild reductive degradation of all but the most hindered of peroxides could have significant applications for controlled remediation of explosives or unwanted radical initiators.

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“…It had also been noted that it was dangerous to treat bisperoxide 71 with nitric acid (Figure b) . Although the controlled acid‐mediated decomposition of TATP showed no indications for a radical mechanism, it is at present unclear whether the explosive decomposition by acid involves alkenyl peroxides.…”

Section: Solution Chemistrymentioning

confidence: 99%

Alkenyl and Aryl Peroxides

Klußmann

2017

Chemistry A European J

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Alkenyl and aryl peroxides are a special class of organic peroxides. Under ambient conditions, they are usually short-lived, rapidly decomposing into radicals by homolytic O-O bond cleavage. They play an important role in the chemistry of the lower atmosphere, where they are formed through ozonolysis of alkenes. In the dark, this pathway is considered the major source of hydroxyl radicals, the "detergent of the atmosphere". In solution, alkenyl and aryl peroxides can be formed by various methods and their decomposition can be harnessed synthetically. For example, reactions involving alkenyl peroxides can be used to introduce ketones through radical additions, and nucleophilic aromatic substitution reactions generating aryl peroxides have been used to synthesize phenols. The radicals can also initiate radical polymerization reactions or chain reactions and mediate oxidative coupling by C-H bond functionalization. Knowledge of their chemistry could be helpful for projects generating or utilizing peroxides.

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Factors Influencing Triacetone Triperoxide (TATP) and Diacetone Diperoxide (DADP) Formation: Part 2

Cited by 21 publications

References 16 publications

The Potential of Isotope Ratio Mass Spectrometry (IRMS) and Gas Chromatography‐IRMS Analysis of Triacetone Triperoxide in Forensic Explosives Investigations

The Potential of Isotope Ratio Mass Spectrometry (IRMS) and Gas Chromatography‐IRMS Analysis of Triacetone Triperoxide in Forensic Explosives Investigations

Reductive Cleavage of Organic Peroxides by Iron Salts and Thiols

Alkenyl and Aryl Peroxides

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