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The photolytic or oxidative liberation of a cyclic (amino)(alkyl)carbene (CAAC)-stabilized arylborylene in the presence of organoazides yielded borylene-organoazide complexes (4a,b) has been achieved in a manner akin to the first step of the Staudinger reaction. Similarly, a CAAC-stabilized aminoborylene also afforded borylene-organoazide complexes (6a–c), which further undergo rearrangement to produce aminoborane triazene species (7a,b). [ABSTRACT FROM AUTHOR]

This study explores the potential of paracetamin, an amine derivative of paracetamol, pronounced for its versatility as an intermediate for dye synthesis and biological application in addressing bacterial resistance. Here, a new series of halogenated triazene derivatives obtained through N-coupling reactions of paracetamin with halogenated aniline derivatives at ortho, meta, and para positions with a moderate yield of 19–72% were discussed. Antibacterial activity of these compounds evaluated against Staphylococcus aureus and Escherichia coli via Kirby–Bauer disc diffusion method observed that four of the compounds bearing fluoro-, chloro-, and bromo-substituents at meta as well as para-bromo substituted triazene displayed a great inhibition zone of 9–12 mm against both strains with ampicillin as its positive control. The structure–activity relationship through molecular docking analyses on CrtM and DNA gyrase enzymes revealed the binding scores of –7.1 to –8.3 and –8.3 to –8.6 kcal/mol respectively, highlighting the significant contribution of hydrogen bonding, hydrophobic and van der Waals interactions towards the binding affinity. Furthermore, the drug-likeness potential of the compounds was assessed through in silico ADMET and Lipinski's rule of five where all compounds adhere and screened to have great pharmacokinetics properties, and low toxicity of 0.360–0.682 for particularly bromo substituted triazene derivatives outlining their potential drug bioavailability. [ABSTRACT FROM AUTHOR]

The conceptual replacement of nitrogen with phosphorus in common organic functional groups unlocks new properties and reactivity. The phosphorus‐containing analogues of triazenes are underexplored but offer great potential as flexible and small bite‐angle ligands. This manuscript explores the synthesis and characterisation of a family of air‐stable azophosphine‐borane complexes, and their subsequent deprotection to the free azophosphines. These compounds are structurally characterised, both experimentally and computationally, and highlight the availability of the phosphorus lone pair for coordination. This is confirmed by demonstrating that neutral azophosphines can act as ligands in Ru complexes, and can coordinate as monodentate or bidentate ligands in a controlled manner, in contrast to their nitrogen analogues. [ABSTRACT FROM AUTHOR]

The syntheses of side‐on Ti(III) triazenido complexes via the ethylene complexes Cp*Ti(η2‐C2H4)(η5‐C5H4CR2H) and side‐on Ti(IV) triazenido complexes via bis(π‐η5 : σ‐η1‐pentafulvene) titanium complexes are reported. The deprotonation of the triazene N−H function occurs under mild conditions either by reduction of the proton to hydrogen mediated via the masked titanocene (II) of the ethylene complex or by the nucleophilic Cexo atom of the pentafulvene moiety. The structures of the paramagnetic Ti(III) complexes were confirmed by single‐crystal X‐ray diffraction, whereas the diamagnetic Ti(IV) complexes were characterized via NMR spectroscopy and additionally, Ti2 c by single‐crystal X‐ray diffraction. The structure of complex Ti2 c reveals one of the smallest bent angles known for titanium pentafulvene complexes. [ABSTRACT FROM AUTHOR]

This work reports the one-pot synthesis of sterically demanding aniline derivatives from aryllithium species utilising trimethylsilyl azide to introduce amine functionalities and conversions to new examples of a common N,N′-chelating ligand system. The reaction of TripLi (Trip = 2,4,6-iPr3-C6H2) with trimethylsilyl azide afforded the silyltriazene TripN2N(SiMe3)2 in situ, which readily reacts with methanol under dinitrogen elimination to the aniline TripNH2 in good yield. The reaction pathways and by-products of the system have been studied. The extension of this reaction to a much more sterically demanding terphenyl system suggested that TerLi (Ter = 2,6-Trip2-C6H3) slowly reacted with trimethylsilyl azide to form a silyl(terphenyl)triazenide lithium complex in situ, predominantly underwent nitrogen loss to TerN(SiMe3)Li in parallel, which afforded TerN(SiMe3)H after workup, and can be deprotected under acidic conditions to form the aniline TerNH2. TripNH2 was furthermore converted to the sterically demanding β-diketimines RTripnacnacH (=HC{RCN(Trip)}2H), with R = Me, Et and iPr, in one-pot procedures from the corresponding 1,3-diketones. The bulkiest proligand was employed to synthesise the magnesium hydride complex [{(iPrTripnacnac)MgH}2], which shows a distorted dimeric structure caused by the substituents of the sterically demanding ligand moieties. [ABSTRACT FROM AUTHOR]

Triacsins are an intriguing class of specialized metabolites possessing a conserved N-hydroxytriazene moiety not found in any other known natural products. Triacsins are notable as potent acyl-CoA synthetase inhibitors in lipid metabolism, yet their biosynthesis has remained elusive. Through extensive mutagenesis and biochemical studies, we here report all enzymes required to construct and install the N-hydroxytriazene pharmacophore of triacsins. Two distinct ATP-dependent enzymes were revealed to catalyze the two consecutive N-N bond formation reactions, including a glycine-utilizing, hydrazine-forming enzyme (Tri28) and a nitrite-utilizing, N-nitrosating enzyme (Tri17). This study paves the way for future mechanistic interrogation and biocatalytic application of enzymes for N-N bond formation.

The chemistry of alkynyl triazenes is an emerging field for organic chemists and especially acid‐induced nucleophilic functionalizations, either directly, or after a prior reaction towards aromatic triazenes under extrusion of nitrogen, paved the way for fruitful strategies. In contrast, the chemical behavior of alkynyl triazenes upon irradiation with light is still unknown. Herein we present the first photoactivation of alkynyl triazenes that triggers an uncommon reactivity pattern involving the cleavage of the N1−N2 bond of the triazene moiety resulting in a unique approach to cyanocarbenes from a readily available, stable, and insensitive precursor. This allows to access various nitrile compounds without the use of a toxic cyanating agent by exploiting the reactivity pattern of carbenes. By variation of the reaction conditions and light sources, different substitution patterns can be obtained selectively in good yields under mild and metal‐free conditions, thus introducing the alkynyl triazene unit as a photo accessible methylene nitrile synthon. Using this synthon, subclasses like α‐alkoxynitriles, α‐aminonitriles and α‐cyanohydrazones become easily available. These exhibit synthetically valuable substitution patterns for the synthesis of pharmaceuticals, intermediates for total synthesis and amino acid synthesis. [ABSTRACT FROM AUTHOR]

An efficient, facile and practical protocol to synthesize various biaryl analogues by the homocoupling of aryl triazenes promoted by guanidinium ionic liquids via copper catalysis has been demonstrated. The three different guanidinium ILs has been employed as solvent/promoter. Several moderate to strong electron‐withdrawing groups and electron‐donating groups are well tolerated by this protocol. The predictive mechanism demonstrating the Cu‐catalytic cycle and role of GIL as promoter. This methodology provides the corresponding products in good yields under moderate reaction conditions with potential for recycling and reuse of the GIL solvent. [ABSTRACT FROM AUTHOR]

Multidrug resistance (MDR) causes difficulties in the treatment of infections and cancer. Research and development studies have become increasingly important for the strategy of preventing MDR. There is a need for new multitarget drug research and advancement to reduce the development of drug resistance in drug‐drug interactions and reduce cost and toxic effects. This study aimed to determine the effects of multi‐target triazene compounds on antibacterial, antifungal, antiviral, cytotoxic, and larvicidal activities were investigated in vitro. A series of 12 novel of 1,3‐diaryltriazene‐substituted sulfadiazine (SDZ) derivatives were synthesized, and the obtained pure products characterized in detail by spectroscopic and analytic methods (FT‐IR, 1H‐NMR, 13C‐NMR, and melting points). The antibacterial and antifungal activities of these derivatives (AH1‐12) were determined by broth microdilution method. All derivatives have been evaluated in cell‐based assays for cytotoxic and antiviral activities against Modified Vaccinia Virus Ankara. The larvicidal efficacy of these chemical compounds was also investigated by using Lucilia sericata (L. sericata) larvae. Twelve 1,3‐diaryltriazene‐substituted SDZ derivatives (AH1‐12) were designed and developed as potent multitargeted compounds. Among them, the AH1 derivative showed the most antibacterial and antifungal activity. Besides, synthesized derivatives AH2, AH3, AH5, and AH7 showed higher antiviral activity than SDZ. All synthesized derivatives showed higher cytotoxic activity than SDZ. Also, they showed larvicidal activity at 72 h of the experiment. As a result, these compounds might be great leads for the development of next‐generation multitargeted agents. [ABSTRACT FROM AUTHOR]

Context: Triazene compounds (-NNN(H)-) exhibit versatility in biological, physical, and chemical applications. In their anionic form (-NNN-)(-), they can act as coordinating sites for metals, forming metallic complexes. In this study, two new isomeric triazene compounds with meta- and para-substituents in their neutral and anionic forms were investigated. A combination of detailed experimental spectroscopic characterization and computational chemistry analyses were employed. The new compounds, 1-(2-benzamide)-3-(3-nitrophenyl) triazene (m-TZN) and 1-(2-benzamide)-3-(4-nitrophenyl) triazene (p-TZN), were compared to 1,3-diphenyltriazene (dph-TZN) to understand the effects of functionalization and targeted triazene deprotonation. The anionic forms are stable, and our investigation suggests that these new compounds are suitable tridentate ligands that can act as chelating agents for metallic cations in stable complexes, similar to those found in vitamin B12. Methods: The absorption, vibrational, and electronic properties of the newly synthesized triazene compounds were extensively characterized using FT-IR/FT-Raman and UV-Vis spectroscopy. Their distinct molecular properties, intramolecular hydrogen bond effects, stability, and electronic transitions were investigated using the ORCA software. These analyses involved DFT and TD-DFT calculations at the ωB97X-D3/Def2-TZVP level of theory with THF CPCM implicit solvation to determine the molecular topology and electronic structure. The advanced STEOM-DLPNO-CCSD method for excited states was employed, enabling an in-depth analysis of ground and excited-state chemistry, accounting for precise electronic correlation and solvation effects. Explicit THF solvation was tested on the full TD-DFT ωB97X-D3/Def2-TZVP level and using ONIOM on the STEOM calculation. Reactivity was studied using Fukui functions, and action as chelating agents was investigated using GFN-xTB2 and DFT. [ABSTRACT FROM AUTHOR]

A novel approach to chemoselective synthesis of biologically important CF3‐subsituted pyrazolines was developed via a Lewis base catalyzed intermolecular triazene cycloaddition reaction of an array of terminal/internal alkenes with CF3CHN2. This strategy features a catalytic amount of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene, high yields (up to 95 %), wide substrate scope and excellent functional group tolerance (54 examples). Importantly, we preformed scaffold diversification of a panel of known pharmaceuticals, natural products, and bioactive heterocycles to generate the corresponding pyrazoline derivatives with potential broad bioactivities for further development. [ABSTRACT FROM AUTHOR]

Palladium‐catalyzed carbonylation reactions aid as potent tools for the insertion of carbonyl unit(s) in a wide array of molecules possessing vast number of applications in multiple domains. An efficient and facile protocol has been reported for the carbonylative Suzuki (CO−S) and carbonylative Hiyama (CO−H) coupling of aryl triazenes using phenyl boronic acid and triethoxy(phenyl)silane respectively via a Pd‐catalysis in combination with Ionic liquids (ILs). Four different ILs have been employed as solvent/reagent/promotor(s) to afford the targeted products in reasonably good yields. As per the predictive mechanism, an in situ generated N‐Heterocarbene‐Ionicliquid‐Palladium (NHC‐IL‐Pd) species serve as a regenerative catalyst while the N‐formyl saccharin (NFSac), a non‐hazardous and commercially available crystalline compound was used as carbon monoxide (CO) surrogate playing important roles to accomplish the desired products in good yields. [ABSTRACT FROM AUTHOR]

Mesoionic carbenes (MIC) are a popular class of compound that are heavily investigated at the moment. The access to cationic MICs, and the ability of MICs to stabilize radicals are two highly attractive fields that have hardly been explored until now. Here the synthesis and characterisation of three different cationic azide‐substituted 1,2,3‐triazolium salts, used as building blocks for studying their reactivity towards triphenylphosphine are reported, where the reactivity is dependent on the nature of the starting triazolium salt. Furthermore, the cationic triazolium salts were used to develop a series of unsymmetrical MIC‐triazene‐NHC/MIC' compounds, which can be readily converted to the radical form either by electrochemical or chemical methods. These radicals, which display NIR electrochromism, were investigated using a battery of techniques such as electrochemistry, UV/Vis/NIR and EPR spectroelectrochemistry, and theoretical calculations. Interestingly, the MIC plays an important role in the stabilization of the triazenyl radical, particularly in a competitive role vis‐à‐vis their NHC counterparts. These results shed new light on the ability of MICs to stabilize radicals, and possibly also on their π‐accepting ability. [ABSTRACT FROM AUTHOR]

New methods for the synthesis of 1,3-diaryltriazenes and azo dyes from aryl amines are reported. Both methods involve the formation of aryl diazonium intermediates via the transnitrosation of aryl amines with N -nitrososulfonamides. Each two-step transformation may be performed in one reaction vessel at room temperature with no precautions taken to exclude air or moisture. Several triazene and azo dye structures are reported here for the first time, demonstrating the utility of operating the two-step reaction sequence under mild conditions. [ABSTRACT FROM AUTHOR]

Compared to the widely concerned azo bridges (–N＝N–), triazene bridges (–N＝N–NH–) with longer nitrogen chains are also favorable linking units leading to novel energetic materials. In this work, a new family of nitrogen-rich nitrotriazolate-based energetic compounds with a triazene bridge were synthesized and well characterized. The experimental results indicated that most of these new compounds have good thermal stabilities and low sensitivities. Among these, ammonium 5,5′-dinitro-3,3′-triazene-1,2,4-triazolate (3) and potassium 5-nitro-3,3′-triazene-1,2,4-triazolate (7) decomposed at a relatively high temperature (240.6 °C for 3 and 286.9 °C for 7). The impact sensitivities of the obtained compounds ranged from 15 J to 45 J. They also have relatively high positive heats of formation between 667.5 to 817.3 kJ mol−1. The calculated detonation pressures (P) were located between 23.7 and 34.8 GPa, and the calculated detonation velocities (D) were between 8011 and 9044 m s−1. Interestingly, ammonium 5-nitro-3,3′-triazene-1,2,4-triazolate (8) and hydroxylammonium 5-nitro-3,3′-triazene-1,2,4-triazole (10) possessed excellent laser-ignited combustion performance. [ABSTRACT FROM AUTHOR]

Triacsins are a family of natural products having in common an N-hydroxytriazene moiety not found in any other known secondary metabolites. Though many studies have examined the biological activity of triacsins in lipid metabolism, their biosynthesis has remained unknown. Here we report the identification of the triacsin biosynthetic gene cluster in Streptomyces aureofaciens ATCC 31442. Bioinformatic analysis of the gene cluster led to the discovery of the tacrolimus producer Streptomyces tsukubaensis NRRL 18488 as a new triacsin producer. In addition to targeted gene disruption to identify necessary genes for triacsin production, stable isotope feeding was performed in vivo to advance the understanding of N-hydroxytriazene biosynthesis.

An efficient and rapid method of synthesizing 1–3,3‐dimethyl triazenes has been developed. This method involves utilizing in situ generated aryldiazonium tetrafluoroborate salts using substituted aryl amines with "DMF‐DMA" (N,N‐Dimethylformamide‐dimethyl acetal) at room temperature. This reaction achieved good to excellent yields (68–95 %) under ambient conditions with a significantly faster rate. The proposed reaction was screened with various withdrawing, donating, and neutral groups containing aryldiazonium salts, and obtained products were confirmed by 1H, 13C NMR and mass spectroscopy techniques. [ABSTRACT FROM AUTHOR]

Application of conventional and ionic liquid (IL) solvents and reagents in the Hiyama cross‐coupling reactions using triazenes as coupling partners was investigated. The microwave‐assisted and Pd‐catalyzed reactions in ROH/HBF4, ROH/BF3 ⋅ Et2O and in [BMIM][X]/[BMIM(SO3H)][OTf]/[BMIM][F] proved effective and gave respectable isolated yields within minutes. The scope of the Hiyama coupling reaction with triazenes was investigated in these media. The IL reagents and solvents were successfully employed to develop stepwise and sequential/tandem Hiyama‐Suzuki (H−S) and Hiyama‐Heck (H−H) methods. Study of the scope of these transformations led to facile synthesis of libraries of biaryls, hetero‐biaryls, diphenylmethanes, styryl‐biphenyls, and a host of biphenyl‐appended heterocycles. The potential for the recycling/reuse of the IL solvents in the Hiyama reaction, and in stepwise and sequential transformations was also examined. [ABSTRACT FROM AUTHOR]

The bifunctional Lewis acidic ionic liquid (LAIL) catalyzed multicomponent arylsulfonation of phenols with aryl triazenes and DABSO was developed. By using LAILs as redox and Lewis acidic catalysts without any additional promoter or ligand through an N2 extrusion/SO2 insertion sequence, various aryl triazenes were transformed into aryl sulfonyl radicals by coupling with DABSO, and these were then coupled with phenoxy radicals to afford the corresponding diaryl sulfones in good yields. The good functional-group tolerance, gram-scale reaction, and avoidance of the use of SO2 gas further demonstrated the practicality of this arylsulfonation reaction. [ABSTRACT FROM AUTHOR]

We describe the synthesis of so far synthetically not accessible 3,6-substituted-4,6-dihydro-3H-pyrazolo[3,4-d][1,2,3]triazines as nitrogen-rich heterocycles. The target compounds were obtained in five steps, including an amidation and a cyclative cleavage reaction as key reaction steps. The introduction of two side chains allowed a variation of the pyrazolo[3,4-d][1,2,3]triazine core with commercially available building blocks, enabling the extension of the protocol to gain other derivatives straightforwardly. Attempts to synthesize 3,7-substituted-4,7-dihydro-3H-pyrazolo[3,4-d][1,2,3]triazines, the regioisomers of the successfully gained 3,6-substituted 4,6-dihydro-3H-pyrazolo[3,4-d][1,2,3]triazines, were not successful under similar conditions due to the higher stability of the triazene functionality in the regioisomeric precursors and thus, the failure of the removal of the protective group.

The new cyclohexenone derivatives have been synthesized by diazo-coupling reactions using 3,5-diphenylcyclohex-2-en-1-one (2) and hydrazone derivative 3 as versatile scaffolds. The structures of the newly synthesized compounds were smoothly elucidated based upon different spectral techniques. The new compounds which bearing azo, triazene or tetraazene moieties were evaluated as antioxidant and antimicrobial agents. The minimal inhibitory concentrations (MICs) values for the most active compounds in antibacterial activity were evaluated. Compounds 8 and 15 revealed the highest antioxidant activity with inhibition values (53.5%) and (47.8%), respectively. In the case of S. aureus, compound 10 exhibited potent antibacterial activity with (95.8%) AI. In the case of E. coli, compound 10 revealed excellent antibacterial activity with (84.6%) AI. In the case of C. albicans, compounds 10, 12 and 14 revealed the best activities with an activity index (66.7–74.1%). [ABSTRACT FROM AUTHOR]

A strategy for the synthesis of 5-((2-cyanoethyl)-X-amino)-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazol-5-ium-4-ides (X = H; CH2CH2CN; NO2 (4a); CN (4b); CO2Et (4c)) starting from 3-amino-4-azido-1,2,5-oxadiazole was developed. The key step in this strategy is the intramolecular thermolytic cyclization of the azido group and the bis(2-cyanoethyl)triazene group. Removal of the 2-cyanoethyl protecting group from amides 4a–c gave potassium salt of the corresponding nitramide and sodium salts of cyano- and ethoxycarbonylamide. The structure and thermal stability of the synthesized compounds were studied experimentally using multinuclear NMR spectroscopy, X-ray crystallography, thermogravimetry, and differential scanning calorimetry. [ABSTRACT FROM AUTHOR]

A strategy was proposed for the synthesis of 5-(morpholin-4-yl)-N'-sulfonyl-1,2,3-thiadiazole-4-imidamides, as well as previously unknown 2-thiocarbamoylacetimidamides. Their reactions with arylsulfonyl azides were studied. In the case of reactions between dimorpholine derivatives of 2-thiocarbamoylacetimidamides and arylsulfonyl azides, diazo transfer did not occur. Instead, a new process was observed, producing the target molecules in one synthetic step via the formation of triazene intermediate and the elimination of ammonia. [ABSTRACT FROM AUTHOR]

A visible‐light‐induced oxidation of diazenyl‐protected tetrahydroisoquinolines and isoindolines for the synthesis of structurally diverse lactams is developed. The reaction was carried out with Eosin Y‐Na2 as an organic photocatalyst and molecular oxygen as an oxidant, and the desired functionalized N‐aryldiazenyl‐lactams were obtained under mild and transition metal‐free conditions. The utility of this method is showcased by the gram‐scale synthesis and deprotection of the N‐aryldiazenyl‐lactam product. [ABSTRACT FROM AUTHOR]

The endoplasmic reticulum (ER) mediates the folding, maturation, and deployment of the secretory proteome. Proteins that fail to achieve their native conformation are retained in the ER and targeted for clearance by ER-associated degradation (ERAD), a sophisticated process that mediates the ubiquitin-dependent delivery of substrates to the 26S proteasome for proteolysis. Recent findings indicate that inhibition of long-chain acyl-CoA synthetases with triacsin C, a fatty acid analogue, impairs lipid droplet (LD) biogenesis and ERAD, suggesting a role for LDs in ERAD. However, whether LDs are involved in the ERAD process remains an outstanding question. Using chemical and genetic approaches to disrupt diacylglycerol acyltransferase (DGAT)-dependent LD biogenesis, we provide evidence that LDs are dispensable for ERAD in mammalian cells. Instead, our results suggest that triacsin C causes global alterations in the cellular lipid landscape that disrupt ER proteostasis by interfering with the glycan trimming and dislocation steps of ERAD. Prolonged triacsin C treatment activates both the IRE1 and PERK branches of the unfolded protein response and ultimately leads to IRE1-dependent cell death. These findings identify an intimate relationship between fatty acid metabolism and ER proteostasis that influences cell viability.

The X-ray diffraction analysis of products of the interaction between hexanuclear manganese pivalate [Mn6O2Piv10(THF)4] and 1,3-di(4′-pyridyl)triazene (LH) shows the possibility of forming 3D metal organic frameworks (MOFs), in which LH acts as di- and tritopic linkers. It is found that ROH (R = Me, Et, i-Pr, n-Bu) alcohols used as a solvent and the reaction temperature have a significant effect on the compositions and structures of the products formed. [ABSTRACT FROM AUTHOR]

Knowing stability constants for the complexes HgII with extracting ligands is very important from environmental and therapeutic standpoints. Since the selectivity of ligands can be stated by the stability constants of cation–ligand complexes, quantitative structure–property relationship (QSPR) investigations on binding constant of HgII complexes were done. Experimental data of the stability constants in ML2 complexation of HgII and synthesized triazene ligands were used to construct and develop QSPR models. Support vector machine (SVM) and multiple linear regression (MLR) have been employed to create the QSPR models. The final model showed squared correlation coefficient of 0.917 and the standard error of calibration (SEC) value of 0.141 log K units. The proposed model presented accurate prediction with the Leave-One-Out cross validation (Q LOO 2 = 0.756) and validated using Y-randomization and external test set. Statistical results demonstrated that the proposed models had suitable goodness of fit, predictive ability, and robustness. The results revealed the importance of charge effects and topological properties of ligand in HgII - triazene complexation. [ABSTRACT FROM AUTHOR]

Herein, Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes of a previously synthesized triazene ligand, namely, (E)‐2‐(3‐(4‐nitrophenyl)triaz‐1‐en‐1‐yl)benzo[d]thiazole (L), were prepared. The metal:ligand ratio of complexes was determined by molar ratio method, and complexes were synthesized based on the result ratio (1:2 for Co(II), Ni(II), and Zn(II) complexes, and (1:1) for Cu(II) and Mn(II)). The complexes were characterized by infrared (IR) and electron paramagnetic resonance (EPR) spectroscopies, magnetic moment, and/or molar conductance measurements. IR spectra suggested the existence of bidentate binding through the nitrogen atom of the thiazole ring and nitrogen atom of the triazene linkage. Molar conductivities indicated the non‐electrolytic nature of all the complexes. Magnetic moment and EPR of the complexes confirmed their octahedral geometries. Thermal studies were conducted to confirm the structures and analyze the thermal stabilities of the complexes. Activation thermodynamic parameters were determined using the Coats–Redfern and Horowitz–Metzger methods. The calf thymus DNA binding activity was investigated by absorption titration experiments and viscosity measurements, and intrinsic binding constants of complexes range from 4.00 × 105 to 5.00 × 105 M−1. Cytotoxic activities were examined against MCF‐7 and HCT‐116 cell lines. Although all the complexes exhibited reasonable cytotoxic effects, their cytotoxic activities were in the following order: Zn(II) > Cu(II) > Mn(II) > Co(II) > Ni(II). Zn(II) complex showed the highest activity with IC50 values are 2.87 and 1.94 μg ml−1 against MCF‐7 and HCT‐116, respectively. Molecular docking was used to assess the binding affinities of these complexes to colon cancer (3ig7) and breast cancer (1hk7) proteins. Zn(II) complex showed the best docking scores compared with the ligand and other tested complexes. Results of molecular docking well correlated with those of the cytotoxicity experiments. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

A strategy for the synthesis of 5-((2-cyanoethyl)-X-amino)-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazol-5-ium-4-ides (X = H; CH2CH2CN; NO2 (4a); CN (4b); CO2Et (4c)) starting from 3-amino-4-azido-1,2,5-oxadiazole was developed. The key step in this strategy is the intramolecular thermolytic cyclization of the azido group and the bis(2-cyanoethyl)triazene group. Removal of the 2-cyanoethyl protecting group from amides 4a–c gave potassium salt of the corresponding nitramide and sodium salts of cyano- and ethoxycarbonylamide. The structure and thermal stability of the synthesized compounds were studied experimentally using multinuclear NMR spectroscopy, X-ray crystallography, thermogravimetry, and differential scanning calorimetry.

The crystal structure of 1-(4-methylphenyl)-3-(2-(trifluoromethyl)phenyl)triaz-1-ene 1-oxide (L) is monoclinic and has a space group of P21/c with a = 8.066(2) Å, b = 16.740(5) Å, c = 11.730(4) Å, β = 117.76(3)° and Z = 4. In this study, direct procedures were used to solve the crystalline structure of this complex and refine it by full-matrix least-squares to ultimate values of R1 = 0.0610 and wR2 = 0.1661 with 1474 reflections (I > 2σ(I)). The molecule is included in inter-hydrogen bonding with C5–H5 acting as donors and O atoms of N-oxide groups as acceptors (O1······H5) with a distance of 2.638 Å. These results were also confirmed by theoretical studies. The spectrophotometric titrations of the synthesized L with metal ions showed a substantially greater stability constant for its nickel ion complex with a mole ratio equal to 1. Consequently, the ligand was used for the selective extraction and spectrophotometric determining the Ni2+ ion in natural water. Under optimized conditions, the calibrating curve was linear over a nickel concentration range of 9.2 × 10−7–8.4 × 10−3 M. The detecting limit of this method was 6.0 × 10−7 M Ni2+. No considerable interference was found from at least 100 times concentrations of a number of possibly interfering ions. [ABSTRACT FROM AUTHOR]

The aim of this study was to investigate the antibacterial and acetylcholinesterase (AChE) inhibitory activities of 3-(3-(2/3/4-substituted phenyl)triaz-1-en-1-yl)benzenesulfonamides (compounds 1 – 12) and to find out new possible drug candidate molecules since the available agents in clinical use have some limitations. According to the results of antibacterial screening for compounds 1 – 12, most of the synthesized compounds were found to be effective against Gram-positive microorganisms while being ineffective (MIC > 1600 μg/mL) on Gram-negative microorganisms. According to the AChE inhibition results, Ki values of compounds 1 – 12 were in the range of 5 ± 1 – 34 ± 2 nMtoward AChE. Tacrine (TAC) used as a reference drug had Ki value of 4 ± 1 nM toward AChE. The non-substituted derivative compound 1 coluld be considered as a lead compound for this study in terms of AChE inhibitory activity, since its Ki value (5 ± 1 nM) was close to that of the reference drug (TAC). Thus, compound 1 was docked at the binding site of AChE and showed good interaction with the target enzyme, suggesting their possible mechanism of action. [ABSTRACT FROM AUTHOR]

[Display omitted] • Significant inhibitory effect of triazenes against DENV infection of Huh7 cells (1.56-8.45 μM) with low cytotoxicity (100 μM). • Phenyl group at N1 and the pyridine at N3 of the triazene promotes antiviral activity. • Electron-withdrawing groups such as CF 3 , improves the antiviral activity. • Anti-DENV activities and the cytotoxicity of triazenes observed suggest a possible role in targeting infectious disease. Dengue fever is an infectious disease caused by the dengue virus (DENV), an RNA Flavivirus transmitted by the mosquitoes Aedes aegypti and Aedes albopictus widespread in tropical, subtropical and also temperate regions. Symptoms range from a simple cold to a severe, life-threatening haemorrhagic fever. According to the WHO, it affects around 390 million people per year. No antiviral treatment for DENV is available, and the Dengvaxia vaccine is only intended for people over 9 years of age who have contracted dengue one time in the past, and shows serotype-specific effectiveness. There is therefore a crying need to discover new molecules with antiviral power against flaviviruses. The present study was carried out to evaluate the anti-DENV activities and cytotoxicity of triazenes obtained by diazocopulation. Some triazenes were highly cytotoxic (16 , and 25) to hepatocarcinoma Huh7 cells, whereas others displayed strong anti-DENV potential. The antiviral activity ranged from EC 50 = 7.82 µM to 48.12 µM in cellulo, with a selectivity index (CC 50 /EC 50) greater than 9 for two of the compounds (10 , and 20). In conclusion, these new triazenes could serve as a lead to develop and optimize drugs against DENV. [ABSTRACT FROM AUTHOR]

Eight new 4-substituted 1-amino-9,10-anthraquinones containing a primary amino group were syn-the-sized by nucleophilic substitution of bromine in 1-amino-4-bromo-9,10-anthraquinones. 1-Amino-4-[2-(hy-droxy-ethyl)amino]-9,10-dioxo-9,10-dihydroanthracene-2-sulfonic acid containing a biogenic amine fragment (2-aminoethanol) was converted into the corresponding 1-triazenyl derivatives. The structure of the synthesized compounds was determined on the basis of the LC/MS and 13C and 1H NMR data, and their drug likeness was estimated in silico. Compounds with a good drug likeness score were analyzed by DIGEP-Pred, their possible interactions with proteins were simulated using STRING, and their biological activity was interpreted using the Kyoto Encyclopedia of Genes and Genomes. [ABSTRACT FROM AUTHOR]

1,2,3‐Triazolium units are present in various functionalized molecules, including mesoionic carbenes, organocatalysts, and anion recognition receptors. While the oxidative [3+2] cycloaddition of triazenes with alkynes is one of the most efficient methods to construct the 1,2,3‐triazolium skeleton, the effect of reaction parameters and substrate scope in the reaction has not been fully studied. Herein, we developed a practical protocol for the synthesis of 1,2,3‐triazolium salts and significantly expanded the substrate scope of triazenes and alkynes. Also, an efficient method for the deprotonative functionalization of 1,2,3‐triazolium salts was achieved. [ABSTRACT FROM AUTHOR]

Aromatic compounds containing triazenyl groups (N3RR′) have a profound impact on synthetic organic and medicinal chemistry. In contrast, the chemistry of vinyl and alkynyl triazenes was a largely uncharted territory until recently. The situation has changed over the last five years, and it has become apparent that vinyl and alkynyl triazenes are highly interesting compounds with a unique reactivity. The electron‐donating properties of the triazenyl group provide alkynyl triazenes with an ynamide‐like reactivity, which can be exploited in reactions of the triple bond. Vinyl triazenes, on the other hand, can be used for electrophilic vinylation reactions. The foundation for this new triazene chemistry are synthetic pathways which allow preparing vinyl and alkynyl triazenes in few steps from readily available starting materials. In this Minireview, we summarize recent developments in this area. [ABSTRACT FROM AUTHOR]

Multicomponent reactions (MCRs) are powerful tool for the construction of polyfunctional molecules in an operationally simple and atom‐economic manner, and the discovery of novel MCRs requests various building blocks. Herein, triazenyl alkynes were disclosed as versatile building blocks in a multicomponent reaction with carboxylic acids, aldehydes and anilines to furnish β‐amino amides with the achievement of high diastereoselectivity and structural diversity. In this process, triazenyl alkynes were bifunctional so that the alkyne moiety acts as C2 fragment and triazene serves as directing group to modulate the transition state thus achieving high diastereoselectivity, in consistence with DFT calculations. Furthermore, the triazenyl group also enables diverse late‐stage transformation. This protocol opens a new vision for the discovery of building block and rational design of MCRs. [ABSTRACT FROM AUTHOR]

By the interaction of [Er(N(SiMe3)2)3] with HN3Dipp ((N3Dipp)– = N,N′-1,3-bis(2,6-diisopropylphenyl) triazenide) [Er(N3Dipp)(N(SiMe3)2)2] (1) and [Er(N3Dipp)2(N(SiMe3)2)] (2) complexes are obtained. The reaction of 2 with thiophenol gives [Er(N3Dipp)2(SPh)(THF)] complex (3). The structures of the compounds is determined by single crystal Xray diffraction of the following solid phases: 1, 2·C6H6, and 3. [ABSTRACT FROM AUTHOR]

The efficient synthesis of molecular hybrids including a DNA‐intercalating 9‐anilinoacridine (9‐AnA) core and a methyl triazene DNA‐methylating moiety is described. Nucleophilic aromatic substitution (SNAr) and electrophilic aromatic substitution (EAS) reactions using readily accessible starting materials provide a quick entry to novel bifunctional anticancer molecules. The chimeras were evaluated for their anticancer activity. Chimera 7b presented the highest antitumor activity at low micromolar IC50 values in antiproliferative assays performed with various cancer cell lines. In comparison, compound 7b outperformed DNA‐intercalating drugs like amsacrine and AHMA. Mechanistic studies of chimera 7b suggest a dual mechanism of action: methylation of the DNA‐repairing protein MGMT associated with the triazene structural portion and Topo II inhibition by intercalation of the acridine core. [ABSTRACT FROM AUTHOR]

In the present study, novel, 1,3-diaryltriazene-derived triazene compounds were synthesized and tested. Triazenes are versatile and belong to a group of alkylating agents with interesting physicochemical properties and proven biological activities. This study describes the synthesis, molecular and crystalline structure, biological activity evaluation, and antifungal and antimicrobial potentials of 1,3-bis(X-methoxy-Y-nitrophenyl)triazenes [X = 2 and 5; Y = 4 and 5]. The antimicrobial and antifungal activities of the compounds were tested by evaluating the sensitivity of bacteria (American Type Culture Collection, ATCC) and clinical isolates to their solutions using standardized microbiological assays, cytotoxicity evaluation, and ecotoxicity tests. The antimicrobial potentials of triazenes were determined according to their minimum inhibitory concentrations (MICs); these compounds were active against gram-positive and gram-negative bacteria, with low MIC values. The most surprising result was obtained for T3 having the effective MIC of 9.937 µg/mL and antifungal activity against Candida albicans ATCC 90028, C. parapsilosis ATCC 22019, and C. tropicallis IC. To the best of our knowledge, this study is the first to report promising activities of triazene compounds against yeast and filamentous fungi. The results showed the potential utility of triazenes as agents affecting selected resistant bacterial and fungal strains. [ABSTRACT FROM AUTHOR]

In this work, we rationally designed and synthesized two novel triazene-amonafide derivatives 2-(2-(diisopropylamino)ethyl)-5-(3,3-dimethyltriaz-1-en-1-yl)-1H-benzo[de]isoquinoline-1,3(2H)-dione (D-11) and 5-(3,3-diethyltriaz-1-en-1-yl)-2-(2-(diisopropylamino)ethyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione (D-12) as potential antitumor agents. The DNA damage induced by the intercalation mode of D-11 (D-12) towards DNA was electrochemically detected through the construction of efficient biosensors. The consecutive processes of reversible redox of naphthylimide ring and irreversible oxidation of triazene moiety were elucidated on the surface of glassy carbon electrode (GCE) by CV, SWV, and DPV methods. Electrochemical biosensors were obtained through the immobilization of ctDNA, G-quadruplexes, poly(dG), and poly(dA), respectively, on the clean surface of GCE. After the incubation of biosensors with D-11 or D-12, the peaks of dGuo and dAdo decreased prominently, and the peak of 8-oxoGua appeared at +0.50 V, suggesting that the interaction between D-11 (D-12) and DNA could result in the oxidative damage of guanine. Unexpected, the as-prepared DNA biosensor possessed satisfactory anti-interference property and good practicability in real samples. UV-vis and fluorescence spectra, and gel electrophoresis assays were employed to further confirm the intercalation mode of D-11 (D-12) towards DNA base pairs. Moreover, D-11 was proved to exhibit stronger anti-proliferation activity than mitionafide and amonafide against both A549 and HeLa cell lines., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)