Copper(II) Halide Complexes with 1‐tert‐Butyl‐1H‐1,2,4‐triazole and 1‐tert‐Butyl‐1H‐tetrazole

1‐tert‐Butyl‐1H‐1,2,4‐triazole (tbtr) was found to react with copper(II) chloride or bromide to give the complexes [Cu(tbtr)₂X₂]_n and [Cu(tbtr)₄X₂] (X = Cl, Br). 1‐tert‐Butyl‐1H‐tetrazole (tbtt) reacts with copper(II) bromide resulting in the formation of the complex [Cu₃(tbtt)₆Br₆]. The obtained crystalline complexes as well as free ligand tbtr were characterized by elemental analysis, IR spectroscopy, thermal and X‐ray analyses. For free ligand tbtr, ¹H NMR and ¹³C NMR spectra were also recorded. In all the complexes, tbtr and tbtt act as monodentate ligands coordinated by Cu^II cations via the heteroring N⁴ atoms. The triazole complexes [Cu(tbtr)₂Cl₂]_n and [Cu(tbtr)₂Br₂]_n are isotypic, being 1D coordination polymers, formed at the expense of single halide bridges between neighboring copper(II) cations. The isotypic complexes [Cu(tbtr)₄Cl₂] and [Cu(tbtr)₄Br₂] reveal mononuclear centrosymmetric structure, with octahedral coordination of Cu^II cations. The tetrazole compound [Cu₃(tbtt)₆Br₆] is a linear trinuclear complex, in which neighboring copper(II) cations are linked by single bromide bridges.     

Synthesis of ribosylated 1,2,3‐triazole derivatives

Ribosylated 1,2,3‐triazole 4 and 5 were synthesized in moderate yields by the reaction of aroyl‐substituted heterocyclic ketene aminals 1 or 2 with 2,3,5‐tri‐O‐benzoyl‐β‐D ‐ribofuranosyl azide ( 3 ). Their structures were determined by elemental analyses and spectroscopic methods. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:487–490, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10167     

Energetic Materials with Promising Properties: Synthesis and Characterization of 4,4′‐Bis(5‐nitro‐1,2,3‐2H‐triazole) Derivatives

Using a variety of functionalization strategies, derivatives of 4, 4′‐bis(5‐nitro‐1,2,3‐2H‐triazole) were designed, synthesized, and characterized. The isomers were separated, their structures were confirmed with single‐crystal X‐ray analysis, and their properties were determined by differential scanning calorimetry, density, impact sensitivity, heat of formation, and detonation velocity and pressure (calculated by EXPLO5 V6.01). Those materials were found to exhibit superior detonation performance when compared with the other fully carbon‐nitrated bis(azoles).     

Unexpected Formation of 5‐Nitro‐1H‐benzimidazoles by Nucleophilic Recyclization of 1‐Methyl‐5‐nitropyridinium Salts

The synthesis of substituted 5‐nitro‐2‐phenyl‐1H‐benzimidazoles has been described via domino anionic process rearrangement of 3‐benzoylamino‐1,2‐dimethyl‐5‐nitropyridinium salts in the presence of NaOH water–alcohol solution. Substituted N‐benzoyl‐o‐phenylenediamines was obtained via recyclization of 3‐benzoylamino‐1,2‐dimethyl‐5‐nitropyridinium salts in the presence of aqueous methylamine solution.     

1‐Butyl‐3‐methyl Imidazolium Acetate Catalyzed Synthesis of N‐substituted‐5‐arylidene‐rhodanines

A direct method for the synthesis of N‐substituted‐5‐arylidene‐rhodanines has been reported in high yield via [bmim]OAc‐catalyzed one‐pot four‐component domino Knoevenagel condensation of primary amine, carbon disulfide, ethyl chloroacetate, and aromatic aldehyde under neat condition. The catalytic role of [bmim]OAc is due to the acidic nature of C‐2 hydrogen of bmim cation and the basic nature of acetate anion in the noncovalent interactions. The synthetic methodology is simple and offers a wide scope for the synthesis of N‐substituted‐5‐arylidene‐rhodanines.     

New polyelectrolytes based on 4‐vinyl‐1,2,3‐triazole and 1‐vinylimidazole

Copolymers of 4‐vinyl‐1,2,3‐triazole and 1‐vinylimidazole (VI) were obtained by radical copolymerization of (4‐vinyl‐1H‐1,2,3‐triazol‐1‐yl)methyl pivalate with VI followed by alkali hydrolysis. Reactivity ratios of the triazole and imidazole monomers are 0.51 and 0.30, respectively. Theoretical quantum‐chemical calculations by the PM3 semiempirical method give close values, which show that the obtained reactivity ratios reflect the activity of the vinyl groups. Polyelectrolyte properties of the copolymers were studied by potentiometric titration. Hydrogen bonds between the protonated triazole cycle and the triazole or imidazole units were found to considerably influence the solubility and solution properties of the copolymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

The Synthesis of Some New N‐[1‐(2,5‐Dichlorophenyl)‐5‐Methyl‐1,2,3‐Triazol‐4‐yl]‐Carbamic Acid Ester Derivatives

The synthesis of some new N‐[1‐(2,5‐dichlorophenyl)‐5‐methyl‐1,2,3‐triazol‐4‐yl]‐carbamic acid ester derivatives are reported in this paper. The yielded products 6a‐l were confirmed by Elemental analyses, NMR, MS, and IR spectra.     

Soluble Polyimides from a New Dianhydride: 5′‐tert‐Butyl‐m‐terphenyl‐3,4,3″,4″‐tetracarboxylic Acid Dianhydride

A novel tert‐butyl‐containing dianhydride was prepared from readily available reagents. It was reacted with various aromatic diamines to prepare a set of polyimides containing tert‐butyl pendent groups. The resulting polyimides exhibit high molecular weights (high inherent viscosity), and a combination of desirable properties, such as good solubility in aprotic amide solvents and cresols, high glass transition temperatures (up to 320 °C), high thermal resistance, film‐forming capability and good mechanical properties.

     

Synthetic and Structural Studies on Methyl‐, tert‐Butyl‐ and Phenylmercury(II) Azide

The reaction of organomercury(II) halogenides (RHgHal, Hal = Cl, I) with silver azide furnished the corresponding covalent organomercury(II) azides RHgN₃ (R = Me ( 1 ), tBu ( 2 ), Ph ( 3 )). In addition to the characterization by multinuclear NMR spectroscopy, IR and Raman spectroscopy as well as mass spectrometry, the mercury content was determined. A dependance on the solventpolarity for the ¹⁴N NMR resonances was observed. Furthermore, X‐ray diffraction studies were performed and the crystal structures for mercury(II) azides 1 – 3 are reported. A comparison of the bond lengths and angles with data from theoretical calculations is given.     

Syntheses and Crystal Structures of Copper(II) and Silver Complexes with 5‐Methyl‐1‐(4‐Methylphenyl)‐1,2,3‐Triazol‐4‐Carboxylic Acid

Two novel complexes [Cu L ₂(MeOH)] ( 1 )and [Ag₂ L (H L )₂(MeOH)] ( 2 ) ( L = 5‐methyl‐1‐(4‐methylphenyl)‐1,2,3‐triazol‐4‐carboxylic acid) were synthesized and characterized by elemental analysis, IR and X‐ray diffraction. Complex 1 is a mononuclear structure; the molecules were assembled into an infinite 2–D supramolecular by the C–H···O weak interactions. Complex 2 is a centrosymmetric dinuclear structure with bis(unidentate) carboxylato co‐ordination mode, and the molecules were assembled into 2–D layers by C–H···O and O–H···O weak interactions.     

Synthesis and Antibacterial Activities of 2‐(1‐Aryl‐5‐Methyl‐1,2,3‐triazol‐4‐yl)‐1,3,4‐Oxadiazole Derivatives

Eighteen novel 2‐(1‐aryl‐5‐methyl‐1,2,3‐triazol‐4‐yl)‐1,3,4‐oxadiazole derivatives and two acylhydrazone intermediate compounds were synthesized by various pathways starting from 1‐aryl‐5‐methyl‐1,2,3‐triazol‐4‐formhydrazide ( 1 ). All products were identified by spectroscopic analysis, and 2‐(1‐aryl‐5‐methyl‐1,2,3‐triazol‐4‐yl)‐5‐benzalthio‐1,3,4‐oxadiazole was further validated by X‐ray crystallography. Results from primary antibacterial activity tests indicated that most of the compounds were effective against E. coli, P. aeruginosa, B. subtilis and S. aureus.     

Synthesis of 2(5H)‐Furanone Derivatives with Bis‐1,2,3‐triazole Structure

A series of new chiral 2(5H)‐furanone derivatives containing bis‐1,2,3‐triazole moiety were designed and synthesized from (5S)‐5‐alkoxy‐3,4‐dihalo‐2(5H)‐furanones 1 , dicarboxyl amino acids 2 , propargyl bromide, and organic azides 5 under mild conditions via the sequential three steps, including asymmetric Michael addition‐elimination, substitution and no‐ligand click reaction. Twelve new intermediates, including N‐[5‐alkoxy‐2(5H)‐furanonyl] dicarboxyl amino acids 3 and their corresponding propargyl esters 4 , and twelve target molecules 6 were characterized by FTIR, ¹H NMR, ¹³C NMR, MS and elemental analysis. The influences of different synthetic conditions and substrates in each step were investigated. The research provides a new method and idea for the synthesis of 2(5H)‐furanone compounds with polyheterocyclic structure due to the diversities of four basic unit molecules.     

Combining the Advantages of Tetrazoles and 1,2,3‐Triazoles: 4,5‐Bis(tetrazol‐5‐yl)‐1,2,3‐triazole, 4,5‐Bis(1‐hydroxytetrazol‐5‐yl)‐1,2,3‐triazole,and their Energetic Derivatives

In the development of new energetic materials, the main challenge is the combination of high energy content with chemical and mechanical stability, two properties that are often contradictory. In this study, the syntheses and comprehensive characterizations of 4,5‐bis(tetrazole‐5‐yl)‐1,2,3‐triazole and the novel 4,5‐bis(1‐hydroxytetrazole‐5‐yl)‐1,2,3‐triazole, as well as their energetic properties, are presented, combining the advantages of the more energetic tetrazole and the more stable 1,2,3‐triazole rings. Nitrogen‐rich salts of both compounds were synthesized to investigate their detonation performances and combustion behavior calculated by computer codes for potential application in erosion‐reduced gun propellant mixtures due to their high nitrogen content. The structures of several of the compounds were studied by single‐crystal X‐ray diffraction and, especially in the case of 4,5‐bis(tetrazol‐5‐yl)‐1,2,3‐triazole, revealed the site of deprotonation.     

Synthesis of Boltorn 1,2,3‐triazole dendrimers by click chemistry

Second‐, third‐, and fourth‐generation hyperbranched aliphatic polyols namely Boltorn® H20, Boltorn H30, and Boltorn H40 were endcapped with azido and activated acetylenic groups in good to excellent yields (75–95%) following an acid catalyzed procedure. The resultant terminally functionalized dendritic azido and acetylenic groups undergo 1,3‐dipolar cycloaddition using methyl (or ethyl) propiolate and benzyl azide, respectively, under catalytic or noncatalytic conditions below 40 °C to yield 1,2,3‐triazole dendrimeric polymers in 82–95% yield, under extremely mild conditions that could be applied for compounds sensitive to acid, base, or heat. The dendritic azido and activated acetylenic derivatives may act as novel scaffolds to tune the mechanical properties of different polymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3748–3756, 2009     

2‐[2‐Methyl‐5‐nitro‐4‐(phenyl­sulfonyl­methyl)­imidazol‐1‐yl]­ethanol and 2‐methyl‐5‐nitro‐4‐phenyl­sulfonyl­methyl‐1,3‐thia­zole

The title compounds, C₁₃H₁₅N₃O₅S and C₁₁H₁₀N₂O₄S₂, respectively, both contain a phenyl­sulfonyl group connected, through a methyl­ene bridge, to either a substituted nitro­imidazole or nitro‐1,3‐thia­zole ring. In the imidazole‐containing mol­ecule, the nitro and sulfonyl groups are trans relative to the sulfonyl–methyl bond, while in the thia­zole‐containing mol­ecule, these substituents are cis. The stabilizing interactions within the crystals are also different between the two compounds.     

Synthesis,Bioactivities and Structure Activity Relationship of N‐4‐Methyl‐1,2,3‐thiadiazole‐5‐carbonyl‐N′‐phenyl Ureas

Twenty nine novel N‐4‐methyl‐1,2,3‐thiadiazole‐5‐carbonyl‐N′‐phenyl ureas were designed and synthesized, and their structures were confirmed by proton nuclear magnetic resonance (¹H NMR), infra red spectroscopy (IR) and high‐resolution mass spectroscopy (HRMS). Compounds V‐9 , V‐11 , V‐12 , V‐15 , V‐19 , V‐21 , V‐22 and V‐24 exhibit excellent activity against Culex pipiens pallens. Compounds V‐12 and V‐22 present good insecticidal activity against Plutella xylostella L. Their median lethal concentrations (LC₅₀) are 164.15 and 89.69 mg·L^?1, respectively. Compound V‐11 also has potential wide spectrum of fungicide activity. Its median effective concentrations (EC₅₀) detected from 3.82 µg·mL^?1 against Physalospora piricola to 31.60 µg·mL^?1 against Cercospora arachidicola. Compounds V‐15 and V‐24 show outstanding induction activities as same as positive controls TDL and ningnanmycin, furthermore V‐24 has the highest induction activity of 41.85%±4.43%. To elucidate the structure activity relationship in these compounds, a 3D‐QSAR model has been built. The established model showed a reliable predicting ability with q² values of 0.643 and r² values of 0.982.     

Proton conducting polymers containing 1H‐1,2,3‐triazole moieties

Polyacrylates containing a different number of 1H‐1,2,3‐triazole groups per repeat unit have been synthesized via conventional free radical polymerization. These polymers were characterized by nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Proton conductivity measurements were made using impedance spectroscopy. Introduction of more than one triazole per repeat unit did not result in an increase in conductivity as there was an accompanying increase in glass transition temperature (T_g). A maximum conductivity of 17.5 μS/cm was obtained at 200 °C under anhydrous condition. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 188–196, 2009