Polycyclic <italic>N</italic>-oxides were developed based on the heterocycles 1,2,4,5-tetrazine and 4<italic>H</italic>,8<italic>H</italic>-difurazano[3,4-<italic>b</italic>:3′,4′-<italic>e</italic>]pyrazine.

The sensitivity of explosives is controlled by factors that span from intrinsic chemical reactivity to mesoscale structure, and has been a topic extensive study for over 50 years.

The treatment of LiAlH4 with 2, 3, or 4 equiv the 3,5-disubstituted pyrazoles Ph2pzH iPr2pzH afforded [Li(THF)2][AlH2(Ph2pz)2] (97%), [Li(THF)][AlH(Ph2pz)3] (96%), [Li(THF)4][Al(Ph2pz)4] (95%), and [Li(THF)][AlH(iPr2pz)3] (89%). ZnCl2 Zn(AlH(Ph2Pz)3)H (70%). X-ray crystal structures these complexes demonstrated κ2 κ3 coordination aluminum-based ligands to Li Zn ions. MgBr2 CoCl2 in THF/Et2O solutions, by contrast, pyrazolate transfer products Mg2Br2(Ph2pz)2(THF)3·2THF (25%)...

Nitrogen-rich hydrotris(tetrazolyl)borate salts of lithium, sodium, and potassium have been prepared for the first time by thermolysis borohydride ion with three equivalents tetrazoles in ether solvents at 160–162 °C. Despite high nitrogen contents, these complexes low sensitivity to impact, electrostatic discharge, friction. As a service our authors readers, this journal provides supporting information supplied authors. Such materials are peer reviewed may be re-organized online delivery,...

Abstract The reaction of 3,4‐dinitropyrazole, 5‐nitrotetrazole, or 4‐nitro‐1,2,3‐triazole with 1,2,4,5‐tetrazines substituted 3,5‐dimethylpyrazolyl (dmp) groups results in energetic cocrystals after 1 minute reflux and cooling to room temperature yields 89–92 %. Hydrogen‐bonding between the dmp group N−H heterocycles are predominant interaction that stabilizes new cocrystals. Each cocrystal packs a different lattice structure sheet‐like herring‐bone crystal packing orientations less...

We report the nitration of tris(hydroxymethyl)aminomethane to tris(nitromethyl)-aminomethane (2) and its corresponding hydrogen chloride (3) bromide (4) salts. While both 3 4 conglomerate into tetramers, there are significant differences in packing those tetrameric units. In units arrange a hexagonal pattern, but adopt alternating orientations leading severe interlocking alkyl nitrate groups. This ultimately leads 2-fold decrease mechanical sensitivity relative suggests that utilizing anion...

We have prepared energetic nitrate ester derivatives of 1,2,4,5-tetrazine and 1,2,4-triazolo[4,3-b]-[1,2,4,5]-tetrazine ring systems as model compounds to study the electrochemical behavior tetrazines in presence explosive groups. The showed lower thermal stabilities relative PETN (pentaerythritol tetranitrate), but slightly improved mechanical sensitivities. electron-rich amine donors leads a cathodic shift tetrazine redox potentials those previously reported explosives. At these...

3,4- and 3,5-Dinitropyrazoles (DNPs) were substituted with acryl allyl groups on the N1 nitrogen atom, resulting in three novel energetic materials. These compounds are all liquids at room temperature melting points ranging from -60.2 to -38.6 °C fully characterized by high-resolution mass spectrometry, elemental analysis, proton carbon nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy. materials also tested for electrostatic discharge, friction, impact...

A 1:2 cocrystal of 4H,8H-difurazano[3,4-b:3′,4′-e]pyrazine and hydroxylamine has been prepared that displays 1,3,5-triamino-2,4,6-trinitrobenzene-like sensitivity performance. Most notably, the detonation properties are better than hypothetical physical mixture also higher theoretically predicted salt, making this a rare example in which synergistic. This was achieved through maximizing intermolecular interactions several hydrogen bonding π-stacking.

Explosives exist in and are expected to withstand a variety of harsh environments up including ionizing radiation, though little is known about the chemical consequences exposing explosives an radiation field. This study focused on radiation-induced changes common energetic functional groups by utilizing consistent molecular backbone. Dodecane was substituted with azide, nitro, nitrate ester, nitramine γ-irradiated 60Co order how group degraded along what relative stability was. Chemical...

Understanding the factors that influence sensitivity is critical for design and screening of new energetic molecules materials, but it often difficult to isolate a single variable analyze its effect. Pentaerythritol tetranitrate (PETN) very common nitrate ester explosive has been widely studied due use in military commercial explosives. We have developed PETN derivatives with modified characteristics by substituting -CCH2ONO2 moiety other substituents, including -CH, -CNH2, -CNH3X, -CCH3, or...

Abstract A 1,2,4‐triazine based azidoxime was formed via the substitution of a chloroxime ( 3 ) with sodium azide in ethanol. This compound characterized single‐crystal X‐ray diffraction. material has calculated density 1.746 g ⋅ cm −3 and is less sensitive to impact, spark, friction, as compared PETN RDX. The dehydrated 1.823 detonation pressure velocity 4 are be 29.1 GPa 8.67 km s −1 , respectively.

Until now, it has been assumed that the primary decomposition pathway for liquid plasticizer bis(2,2-dinitropropyl)acetal and bis(2,2-dinitropropyl)formal (BDNPA/F) was nitrous acid elimination (NAE). An ultrahigh-performance chromatography (UHPLC) coupled to quadrupole time-of-flight mass spectrometry (QTOF) methodology developed discover identify degradation products of BDNPA/F. No evidence NAE found. However, two other pathways were found: (1) hydrolysis acetal/formal functional group (2)...

The dialumane [Al2][Na(Ph2pz)3]2 () has been prepared by the reaction of Na(Ph2pz) with a metastable solution AlCl. structure contains two hydrotris(pyrazolyl)borate-like Na(Ph2pz)3(2-) moieties that are coordinated to each Al atom in κ(2),κ(1)-N,N,N fashion and several π-stacking interactions present between pyrazolate phenyl rings. In ligands dynamic exchange, even at -80 °C, which shows lability these low-valent aluminum centers.

Pentaerythritol tetranitrate (PETN) is a very common nitrate ester explosive that has been widely studied due to its use in military and commercial explosives. Recent experimental work calculations have shown substituting the central carbon atom of PETN with silicon results an extremely sensitive contact explosive. We attempted develop derivatives which are less sensitive, by attaching hydrogen, amino, methyl groups atom, (and one -CH2ONO2 group) phosphorous oxide. relate handling...

High nitrogen compounds find wide use in the development of new propellants and explosives as well pharmaceutical chemistry bioisosteres, bacterial stains, antifungal agents. A class underexplored high-nitrogen materials includes azidoximes their 1-hydroxytetrazole isomers. Azidoximes possess an energetic azide group are quite sensitive to impact, spark, friction. Therefore, these generated situ cyclized under mild acidic conditions Recently, we synthesized a novel 1,2,4-triazine-derived...

An energetic nitrate ester acrylate monomer (4) was synthesized in a total yield of 68% and polymerized to form the polymer (NEAP). Compound 4 is liquid at room temperature with melting point -8.6 °C NEAP solid glass-transition -8.8 °C. Intermediates leading were characterized by high-resolution mass spectrometry, elemental analysis, Fourier transform infrared spectroscopy, proton carbon nuclear magnetic resonance spectroscopies (1H 13C{1H} NMR). Both have electrostatic discharge, friction,...

Energetic plasticizers are being sought for their use in energetic formulations when combined with explosives. An plasticizer based on the insensitive highly explosive 3-amino-5-nitro-l,2,4-triazole (ANTA) was synthesized and characterized by spectroscopy, X-ray crystallography, thermal analyses, safety testing. Lastly, density functional theory calculations were employed to examine observed selectivity among three nucleophilic ring nitrogen atoms of ANTA toward electrophiles such as...

The impact of relative humidity (RH) on organic new particle formation (NPF) from ozonolysis biogenic volatile compounds (BVOCs) remains an area active debate. Previous reports provide contradictory results indicating both depression and enhancement NPF under conditions high RH. Herein we report the RH dark cis-3-hexenyl acetate (CHA), a green-leaf (GLV) emitted by vegetation. We show that inhibits this BVOC, essentially shutting it down at levels &gt; 1 %. While mechanism for inhibition...

Abstract Two novel cyclic Al 3 clusters, Li 2 [Al (PR ) 6 ] ⋅ 2(Et O) [R=Ph ( 1 ), Cy )] were synthesized through salt metathesis of metastable AlCl (Et n solutions with LiPR . Both complexes characterized by single crystal X‐Ray diffraction and their solid state electronic structures are compared to previously reported clusters. Compounds further using density functional theory (DFT) methods understand the nature free electron three‐center two‐electron Al−Al bonds. Calculations revealed...