ChemInform Abstract: METHYLATION OF 3‐NITRO‐1,2,4‐TRIAZOL‐5‐ONE

Kofman, T. P.; Pevzner, M. S.; Zhukova, L. N.; Кравченко, Т. А.; Frolova, Galina M.

doi:10.1002/chin.198024180

Cited by 9 publications

(14 citation statements)

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“…Therefore, if different species are present in the pH 5-9 range, testing should be conducted at 2-3 pH values throughout the pH 5-9 range. NTO is an ionizable compound ( Figure 19) with a pKa of 3.67 (Kofman et al 1980). A pH of 1 ppm NTO solution in deionized water equals to a pH of 4.98.…”

Section: Phototransformation Of Nto and Dnan In Solutionmentioning

confidence: 99%

Dissolution of NTO, DNAN, and Insensitive Munitions Formulations and Their Fates in Soils

Dontsova¹,

Taylor²,

Pesce‐Rodriguez³

et al. 2014

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New explosive compounds that are less sensitive to shock and high temperatures are being tested as replacements for TNT and RDX. Two of these explosives, DNAN (2,4-dinitroanisole) and NTO (3-nitro-1,2,4-triazol-5one), have good detonation characteristics and are the main ingredients in a suite of insensitive munitions (IM) explosives that are being, or soon will be, fielded. Both compounds, however, are more soluble than either TNT or RDX; and research has shown that both have some human and environmental toxicity. Data on their fate is needed to determine if DNAN and NTO have the potential to reach groundwater and be transported off base, an outcome that could create future contamination problems on military training ranges and trigger regulatory action. In this study, we measured how quickly DNAN and NTO dissolve in IM formulations and how solutions of these IM explosives interact with different types of soils. Because both dissolution and solution-soil interactions are determined by a suite of parameters, we are using a multifaceted approach to studying these processes. Given a mass of IM compounds scattered on the range, our work will help determine the dissolved IM masses, their subsequent transport and fate, and their likelihood of reaching groundwater. DISCLAIMER: The contents of this report are not to be used for advertising, publication, or promotional purposes. Citation of trade names does not constitute an official endorsement or approval of the use of such commercial products. All product names and trademarks cited are the property of their respective owners. The findings of this report are not to be construed as an official Department of the Army position unless so designated by other authorized documents.

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Section: Phototransformation Of Nto and Dnan In Solutionmentioning

confidence: 99%

Dissolution of NTO, DNAN, and Insensitive Munitions Formulations and Their Fates in Soils

Dontsova¹,

Taylor²,

Pesce‐Rodriguez³

et al. 2014

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“…One of the most important IMCs is 3-nitro-1,2,4-triazol-5-one (NTO), which is used in the ammunition formulations IMX-101 and IMX-104. NTO has a high water solubility (16 642 mg/L at 25 °C) and is anionic at circumneutral pH (p K a = 3.76). , As a result, NTO is minimally sorbed, highly mobile, and has a great potential to contaminate soil and groundwater at/near military training ranges and munitions manufacturing sites. Improper waste disposal, spills, and incomplete detonation are some of the sources of IMC contamination in the United States and elsewhere. ,, Controlled detonations of IMX-104 mortar rounds showed that up to 1.2 (in high-order detonations) and 50% (in blow-in-place detonations) of the NTO initially present remained as residues on soils .…”

Section: Introductionmentioning

confidence: 99%

“…NTO has a high water solubility (16 642 mg/L at 25 °C) 1 and is anionic 2 at circumneutral pH (pK a = 3.76). 3,4 As a result, NTO is minimally sorbed, 5 highly mobile, and has a great potential to contaminate soil and groundwater at/near military training ranges and munitions manufacturing sites. Improper waste disposal, spills, and incomplete detonation are some of the sources of IMC contamination in the United States and elsewhere.…”

Section: Introductionmentioning

confidence: 99%

Reduction of 3-Nitro-1,2,4-Triazol-5-One (NTO) by the Hematite–Aqueous Fe(II) Redox Couple

Cárdenas-Hernández

Anderson

Murillo-Gelvez

et al. 2020

Environ. Sci. Technol.

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3-Nitro-1,2,4-triazol-5-one (NTO) is an insensitive munition compound (MC) that has replaced legacy MC. NTO can be highly mobile in soil and groundwater due to its high solubility and anionic nature, yet little is known about the processes that control its environmental fate. We studied NTO reduction by the hematite–Fe2+ redox couple to assess the importance of this process for the attenuation and remediation of NTO. Fe2+ (aq) was either added (type I) or formed through hematite reduction by dithionite (type II). In the presence of both hematite and Fe2+ (aq), NTO was quantitatively reduced to 3-amino-1,2,4-triazol-5-one following first-order kinetics. The surface area-normalized rate constant (k SA) showed a strong pH dependency between 5.5 and 7.0 and followed a linear free energy relationship (LFER) proposed in a previous study for nitrobenzene reduction by iron oxide–Fe2+ couples, i.e., log k SA = −(pe + pH) + constant. Sulfite, a major dithionite oxidation product, lowered k SA in type II system by ∼10-fold via at least two mechanisms: by complexing Fe2+ and thereby raising pe, and by making hematite more negatively charged and hence impeding NTO adsorption. This study demonstrates the importance of iron oxide–Fe2+ in controlling NTO transformation, presents an LFER for predicting NTO reduction rate, and illustrates how solutes can shift the LFER by interacting with either iron species.

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“…Under the action of equimolar amounts of dimethyl sulfate and alkali, 4-methyl-3-nitro-1,2,4-triazol-5-one is preferentially formed. With a 4-fold molar excess of alkali, the major product is 1-methyl-3-nitro-1,2,4-triazol-5-one, whereas with a 1 : 2 dimethyl sulfate-to-alkali ratio, 5-methoxy-3-nitro-1,2,4-triazole [2,3]. The appreciable formation of the O-methylation product is also observed in dimethylformamide.…”

mentioning

confidence: 71%

Adamantylazoles: VIII. Acid-catalyzed adamantylation of 1,2,4-triazol-5-ones

et al. 2004

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3-R-1,2,4-Triazol-5-ones are adamantylated in sulfuric acid. The reaction involves the N 1 atom of the ring. 4-Adamantyl-1-methyl-, 1-adamantyl-4-methyl-, and 1,4-diadamantyl-1,2,4-triazol-5-ones were also prepared. Therewith, it was found that N 1 exhibits a higher reactivity than N 4 . Alkylation of 1,2,4-triazol-5-ones and their derivatives in alkaline media has been studied in sufficient detail. Under the action of equimolar amounts of dimethyl sulfate and alkali, 4-methyl-3-nitro-1,2,4-triazol-5-one is preferentially formed. With a 4-fold molar excess of alkali, the major product is 1-methyl-3-nitro-1,2,4-triazol-5-one, whereas with a 1 : 2 dimethyl sulfate-to-alkali ratio, 5-methoxy-3-nitro-1,2,4-triazole [2,3]. The appreciable formation of the O-methylation product is also observed in dimethylformamide. At the same time, no information on alkylation of 1,2,4-triazol-5-ones in acids has so far been available.We have studied acid-catalyzed alkylation of 1,2,4-triazol-5-ones in sulfuric acid using the example of adamantylation. In view of the fact that the concentration of sulfuric acid required to generate 1-adamantyl cation from 1-adamantanol is above 70% [4], all adamatylation reactions were performed in 85% or even more concentrated sulfuric acid.The reaction of 1,2,4-triazol-5-one (I) with 1-adamatanol in 85% sulfuric acid gave 1-adamantyl-1,2,4-triazol-5-one (II) as a single product (yield 84%). The IR spectrum of the product contains a characteristic carbonyl absorption band at 1736 cm !1 , implying the adamantylation by ring nitrogen.

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ChemInform Abstract: METHYLATION OF 3‐NITRO‐1,2,4‐TRIAZOL‐5‐ONE

Abstract: Methylierungen der Titelverbindung (I) mit Dimethylsulfat/NaOH liefern bei Einsatz von 1 Äquivalent Methylierungsreagenz ‐ Gemische der Monomethylderivate (II)‐(IV), bei Einsatz von 2 Äquivalenten Me2SO4/NaOH entstehen überwiegend die Dimethylderivate (V) und (VI).

Cited by 9 publications

References 0 publications

Dissolution of NTO, DNAN, and Insensitive Munitions Formulations and Their Fates in Soils

Dissolution of NTO, DNAN, and Insensitive Munitions Formulations and Their Fates in Soils

Reduction of 3-Nitro-1,2,4-Triazol-5-One (NTO) by the Hematite–Aqueous Fe(II) Redox Couple

Adamantylazoles: VIII. Acid-catalyzed adamantylation of 1,2,4-triazol-5-ones

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