Hydrazinium Salts Research Articles

Polynitro-1,2,4-triazole Energetic Materials with N-Amino Functionalization.

Trinitromethyl and N-amino groups were innovatively incorporated into the framework of 1,2,4-triazole, resulting in 1-amino-5-nitro-3-(trinitromethyl)-1,2,4-triazole (2). Ammonium and hydrazinium salts of 1-amino-5-nitro-3-(dinitromethyl)-1,2,4-triazole were synthesized by acidification, extraction, and neutralization with bases from the potassium salt. All of the newly prepared energetic compounds were comprehensively characterized by using infrared spectroscopy, elemental analysis, nuclear magnetic resonance spectroscopy, and single crystal X-ray diffraction. Compound 2 exhibits favorable properties such as positive oxygen balance (OBCO2 = 5.8%), high density (1.88 g cm-1), good detonation performances (vD = 8937 m s-1, P = 35.5 GPa), and appropriate friction sensitivity (FS = 144 N). The potassium salt 3 demonstrates good thermal decomposition temperature (181 °C) and high density (1.98 g cm-1), while the ammonium salt and hydrazinium salt also display good thermal decomposition temperatures of 183 and 176 °C, respectively. Among these compounds, the ammonium salt exhibits the lowest mechanical sensitivities (FS = 144 N, IS = 6 J).

Insight into the structural and energetic features of substituted triazolofurazans

A comparative study of structures, stability and energetic performance of ammonium and hydrazinium salts of 4H-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazole (triazolofurazan, TF) as well as its N-oxide and N-nitroimide was performed.

Selective Synthesis and Characterization of the Highly Energetic Materials 1-Hydroxy-5H-tetrazole (CHN4 O), its Anion 1-Oxido-5H-tetrazolate (CN4 O- ) and Bis(1-hydroxytetrazol-5-yl)triazene.

For the first time, an adequate selective synthesis, circumventing the formation of 2‐hydroxy‐5H‐tetrazole, of 1‐hydroxy‐5H‐tetrazole (HTO), as well as the synthesis of bis(1‐hydroxytetrazol‐5‐yl)triazene (H3T) are reported. Several salts thereof were synthesized and characterized which resulted in the formation of new primary and secondary explosives containing the 1‐oxidotetrazolate unit. Molecular structures are characterized by single‐crystal X‐ray diffraction, 1H and 13C NMR, IR, and elemental analysis. Calculation of the detonation performance using the explo5 code confirmed the energetic properties of 1‐hydroxy‐5H‐tetrazole. The detonation properties can be adjusted to the requirements for those of a secondary explosive by forming the hydroxylammonium (6) or hydrazinium (7) salts, or to meet the requirements of a primary explosive by forming the silver salt 4, which shows a fast DDT on contact with a flame. The sensitivities of all compounds towards external stimuli such as impact, friction, and electrostatic discharge were measured.

Effect of Terminal Alkylation of Aryl and Heteroaryl Hydrazines in the Fischer Indole Synthesis

The effect of alkylation on the terminal position of aryl and heteroaryl hydrazines in the Fischer indole synthesis was examined. Compared to their unalkylated counterparts, reactions using alkylated hydrazines provided indole products with higher yields and faster rates. The reactions can be conducted at lower temperatures and are compatible with acid-sensitive functionality. The terminally alkylated hydrazines were readily prepared by a new two-step sequence and held as stable hydrazinium salts. The mild formation of the salts along with the favorable Fischer indole reaction conditions highlights the potential of this approach in later-stage synthetic use.

N−N Bond Formation Using an Iodonitrene as an Umpolung of Ammonia: Straightforward and Chemoselective Synthesis of Hydrazinium Salts

AbstractThe formation of hydrazinium salts by N−N bond formation has typically involved the use of hazardous and difficult to handle reagents. Here, mild and operationally simple conditions for the synthesis of hydrazinium salts are reported. Electrophilic nitrogen transfer to the nitrogen atom of tertiary amines is achieved using iodosylbenzene as oxidant and ammonium carbamate as the N‐source. The resulting process is highly chemoselective and tolerant to other functional groups. A wide scope is reported, including examples with bioactive molecules. Insights on the structure of hydrazinium salts were provided by X‐ray analysis.magnified image

Synthesis of Novel Energetic N-(1-Carboxymethyl-1H-tetrazole-5-yl)-hydrazinium Salts

Synthesis of Novel Energetic N-(1-Carboxymethyl-1H-tetrazole-5-yl)-hydrazinium Salts

Energetic Di- and Trinitromethylpyridines: Synthesis and Characterization.

Pyridine derivatives based on the addition of trinitromethyl functional groups were synthesized by the reaction of N2O4 with the corresponding pyridinecarboxaldoximes, then they were converted into dinitromethylide hydrazinium salts. These energetic compounds were fully characterized by IR and NMR spectroscopy, elemental analysis, differential scanning calorimetry (DSC), and X-ray crystallography. These pyridine derivatives have good densities, positive enthalpies of formation, and acceptable sensitivity values. Theoretical calculations carried out using Gaussian 03 and EXPLO5 programs demonstrated good to excellent detonation velocities and pressures. Each of these compounds is superior in performance to TNT, while 2,6-bis(trinitromethyl)pyridine (D = 8700 m·s−1, P = 33.2 GPa) shows comparable detonation performance to that of RDX, but its thermal stability is too low, making it inferior to RDX.

Preparation and Characterization of Some New Hydrazinium Carboxylates

Hydrazinium salts of aromatic carboxylic acids were prepared by neutralization of acid with hydrazine hydrate and characterized by analytical, IR spectral and TG-DTA analysis. All the compounds undergo decomposition yielding carbon residue as the end product. The in vitro antibacterial study of 2,4-dichlorophenoxyacetic acid and its hydrazinium salt against Escherichia Coli have been investigated and the results show that the as-prepared hydrazinium salts have better antibacterial activity than the free acid.

Energetic salts based on furazan-functionalized tetrazoles: routes to boost energy.

Based on the backbone of the furazan-tetrazole structure, routes were developed to improve the properties of energetic materials. Two types of high-density energetic salts were designed, prepared, and fully characterized. Single-crystal X-ray analyses support the structural characteristics for two amino salts. A majority of the salts exhibited good detonation properties, high thermal stabilities, and relatively low impact and friction sensitivities. Hydroxylammonium and hydrazinium salts, 1-3 and 1-4, which have relatively high densities (1.84 and 1.74 g cm(-3,) , respectively), acceptable impact and friction sensitivities (14 J, 160 N and 28 J, 360 N), and good detonation pressures (38.3 and 32.2 GPa) and velocities (9323 and 9094 m s(-1) ), have performance properties superior to 1,3,5-trinitro-1,3,5-triazinane (RDX) and triaminotrinitrobenzene (TATB).

Crystal Structures of Hydrazinium(II) Salts of [SbF6]– and [Sb2F11]–

AbstractN2H6(Sb2F11)2 was synthesized by the reaction of N2H6F2 with excess of SbF5 in anhydrous hydrogen fluoride (aHF). It crystallizes in the triclinic space group P$\bar{1}$ (No. 2) with a = 6.6467(3) Å, b = 8.3039(4) Å, c = 8.3600(5) Å, α = 76.394(5) o, β = 70.161(5) o, γ = 70.797(5) o, V = 405.90(4) Å3 at 150 K, Z = 2. When it is redissolved in aHF, it solvolysis with the release of SbF5 yielding N2H6(SbF6)2 which crystallizes in the monoclinic C2/c space group (No. 15) with a = 7.3805(3) Å, b = 12.3248(5) Å, c = 10.4992(4) Å, β = 92.218(4) o, V = 954.33(7) Å3 at 150 K, and Z = 8. No other phases were observed in crystallization products when different molar ratios of N2H6F2/SbF5 (1:1,2:3,1:3) in aHF were used as starting materials.

Preparation, Characterization, Thermal Degradation, and Crystal Structures of Hydrazinium and Ammonium Salts of Ethylenediaminetetraacetic Acid and Seven Coordinated N2H5[Cd(Hedta)(H2O)].H2O

Dihydrazinium, hydrazinium, hydrazinium ammonium, and ammonium salts of ethylenediaminetetraacetic acid (H4edta) such as (N2H5)2H2edta, N2H6H2edta, N2H5NH4H2edta and (NH4)2H2edta have been prepared and characterized by elemental analyses, hydrazine analysis, conductivity measurements, and infrared spectra. The thermal degradation studies reveal that these compounds undergo complete and multi step decomposition with or without melting. The IR spectra show that in all the cases the acidic protons are attached to the tertiary nitrogen atoms of edta and all the salts exist as zwitterions. The X-ray single-crystal data and the corresponding ORTEP diagram of the dihydrazinium and hydrazonium salts clearly support and confirm the data. Hydrazinium hydrogenethylenediaminetetraacetato aquo cadmium(II) monohydrate, N2H5[Cd(Hedta)(H2O)].H2O, has been synthesized and structurally characterized. The crystal belongs to orthorhombic crystal system and the space group Pbca. The crystal data are the following: a = 9.423 Å, b = 4.406 Å, c = 23.838 Å, α = β = γ = 90°, V = 3236 Å3, Z = 8, Dc = 1.932 Mg/m3, μ = 1.412 mm−1, F(000) = 1904, the final R = 0.0190, and wR = 0.0562 for 3707 observed reflection with I›2σ(I).

A computational study of proton transfer and solvent effect on nitroamino[1,3,5]triazine-based ammonium energetic salts

We have performed dispersion corrected density functional theory calculations to study the proton transfer in the gas-phase and solvent effects on the structural transformation for a series of nitrogen-rich energetic salts. Proton transfer was observed from the cations to anions within all the salts in the gas-phase and resulted into neutral hydrogen-bonding complexes; however, they were stabilized as ionic structures in the liquid state with solvation energies in the range of −37.72–69.37 kJ/mol. An increment by 4–9 Debye in the dipole moment was found when the salts went from the gas to solution. Moreover, these ionic salts exhibited relatively high densities in the range of 1.63–1.96 g/cm3 desirable for energetic materials. A combination of NH3OH+ to the cation and −NO2 or −NF2 group to the anion can improve efficiently the detonation performance. Most of the ammonium, hydroxyammonium, and hydrazinium salts were promising competitive explosives and could be used as potential targets for synthesis.

Crystal Structures, Thermal Degradation, and Biological Activities of Some New Ammonium and Hydrazinium Salts of Cyclohexanediaminetetraacetic Acid

Neutralization reaction in aqueous medium between cyclohexanediaminetetraacetic acid (H4CDTA) and weak bases such as hydrazine hydrate and aqueous ammonia yielded a series of new salts such as N2H5H3CDTA.H2O, (N2H5)3HCDTA.H2O, NH4H3CDTA.2H2O, and N2H5NH4H2CDTA.H2O. The type of salt formed depends on the ratio of H4CDTA to base used and the pH of the medium. The compositions of the previous compounds were determined by hydrazine and microanalyses. The infrared spectra of the salts reveal the presence of free carboxylic acid groups. The X-ray single-crystal structures of N2H5H3CDTA and NH4H3CDTA clearly reveal that these salts exist as zwitterions in solid state. The simultaneous TG-DTA profiles show the multistep degradation with almost 100% mass loss indicating the complete decomposition. The biological screening of the aqueous solution of these salts reflects the enhanced activities of the hydrazinium salts than the free acid and the ammonium salts.

Computer prognosis, synthesis, and psychotropic properties of hydrazinium salts of phosphorylacetohydrazides

Application of computer modeling to a series of phosphorylated carboxylic acid derivatives revealed new compounds possessing high psychotropic activity, i.e., hydrazinium salts of phosphorylacetohydrazides. It was proved experimentally that these compounds contributed to the improvement of memory and learning processes, possessed antihypoxic properties, and exhibited antidepressant activity. The pharmacologically relevant pharmacophores in this group were the methyl and fluorine atom in the phosphoryl aryl radical. The obtained results confirmed the expediency of using a complex analysis of computer modeling of the structure–activity relationship and an experimental search for pharmacophores for scientifically justified prognosis and design of new drugs.

Preparation, Analytical, IR Spectral, and Thermal Studies of Some New Hydrazinium Carboxylates

Hydrazinium salts of 2,4-dichlorophenylacetic acid, phenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, diphenylacetic acid, cinnamic acid, and picolinic and nicotinic acids have been prepared by accomplishing neutralization of aqueous hydrazine hydrate with the respective acids. Formation of these hydrazinium salts has been confirmed by analytical, IR spectral, and thermal studies. IR spectra of the salts register N–N stretching frequencies of ion in the region 963–951 cm−1 and the frequencies of ion in the region 1047–1026 cm−1. Thermal decomposition studies show that the hydrazinium salts undergo melting followed by endothermic decomposition into carbon residue as the endproduct.

Synthesis and Characterization of 5-Amino-1-nitriminotetrazole and Its Salts

New nitrogen-rich energetic compound 5-amino-1-nitriminotetrazole (2) and its ammonium (3), hydrazinium (4) salts have been prepared. Their structures were characterized and confirmed by H-1 NMR spectroscopy, IR spectroscopy, elemental analysis and ESI-MS, X-ray single-crystal diffraction. Compound 2 crystallizes in the orthorhombic Pna2(1) space group with unit cell parameters are a = 9.229(2) , b = 5.5271(13) , c = 10.295(2) , V = 525.1(2) (3), Z = 4. Compound 3 crystallizes in the Monoclinic C2/c space group, its unit cell parameters are a = 25.932 (6) , b = 6.8844(15) , c = 14.006(3) , beta = 102.052(3), V = 2445.3(10) (3), Z = 16. Compound 4 crystallizes in the Monoclinic P2(1)/c space group with unit cell parameters are a = 7.275(3) , b = 14.273(5) , c = 6.802(2) , beta = 97.009(5) , V = 701.0(4) (3), Z = 4. Extensive hydrogen bonds of these compounds packed a 3D network. Finally, the influences of molecular structure on the properties of the new compounds were discussed.

ChemInform Abstract: Product Class 7: Hydrazines and Hydrazinium Salts

AbstractReview: 293 refs.

Synthesis of ferrocenyl pyrazoles by the reaction of 3-ferrocenylpropynal with hydrazinium salts

Synthesis of ferrocenyl-substituted pyrazoles via the reaction between 3-ferrocenylpropynal and hydrazinium salts is described. Depending upon the substitution pattern of hydrazine derivative, the reaction affords 1-alkyl/aryl-5-ferrocenylpyrazoles and/or 1-alkyl/aryl-3-ferrocenylpyrazoles. Structures of 5-ferrocenyl-1-phenyl-1 H-pyrazole, 1-benzyl-5-ferrocenyl-1 H-pyrazole and 2-(3-ferrocenylpyrazol-1-yl)ethanol were identified by X-ray crystallography.

N4H9Cu7S4: A Hydrazinium‐Based Salt with a Layered Cu7S4‐ Framework.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

N4H9Cu7S4: A Hydrazinium-Based Salt with a Layered Cu7S4- Framework

Crystals of a hydrazinium-based copper(I) sulfide salt, N4H9Cu7S4 (1), have been isolated by an ambient temperature solution-based process. In contrast to previously reported hydrazinium salts of main-group metal chalcogenides, which consist of isolated metal chalcogenide anions, and ACu7S4 (A = NH4+, Rb+, Tl+, K+), which contains a more three-dimensional Cu7S4- framework with partial Cu-site occupancy, the structure of 1 [P21, a = 6.8621(4) A, b = 7.9851(4) A, c = 10.0983(5) A, beta = 99.360(1) degrees , Z = 2] is composed of extended two-dimensional Cu7S4- slabs with full Cu-site occupancy. The Cu7S4- slabs are separated by a mixture of hydrazinium and hydrazine moieties. Thermal decomposition of 1 into copper(I) sulfide proceeds at a significantly lower temperature than that observed for analogous hydrazinium salts of previously considered metal chalcogenides, completing the transition at temperatures as low as 120 degrees C. Solutions of 1 may be used in the solution deposition of a range of Cu-containing chalcogenide films.