Tetrazole Group Research Articles

Synthesis of new dyes containing double tetrazole groups for sensitization of TiO2 nanoparticles in dye-sensitized solar cells

Di(1H-tetrazol-5-yl)methane is employed as a new electron acceptor group in the synthesis of two metal-free organic dyes containing triphenylamine donor group. Dye-sensitized nanocrystalline TiO2 solar cell (DSSC) applying these novel dyes is constructed for consideration of their photovoltaic properties. The electronic properties of the dyes are also considered with the aid of theoretical calculations. The DSSC constructed from 4-(2,2-di(1H-tetrazol-5-yl)vinyl)-N,N-diphenylaniline (T1) shows a short-circuit photocurrent density of 13.38 mA cm−2, an open circuit voltage of 578 mV, and a fill factor of 0.54, with a resulted solar energy-to-electricity conversion efficiency of 4.18% under simulated 1 sun irradiation (100 mW cm−2). This result reveals that the dye with the di(1H-tetrazol-5-yl)methane anchoring group injects more electrons to the conduction band of TiO2 in comparison with its analogs with single tetrazole ring in their anchoring group. It is found that in spite of a red-shift of the absorption spectrum resulted from the lengthening of the molecule, the dye with two di(1H-tetrazol-5-yl)methane groups gives lower performance than the dye with a single electron acceptor.

Synthesis, DNA Interaction and Genotoxic Evaluation of a Photoactive Benzothiadiazole with Potential Application in Photovoltaic Paint

A new fluorophore containing 2,1,3-benzothiadiazole unit with alkylated tetrazole terminal groups as electron donors connected through a π-conjugated system of the type (D-π-A-π-D) was synthesized using the Sonogashira coupling reaction with good yields. The genotoxicity of the two intermediate compounds and the final product was evaluated in vitro in consideration of the potential application of the new compound in the chemical production of photovoltaic paints. The new fluorophore did not show significant biological effects in the cell viability test and the comet assay when compared with the intermediate compounds that were obtained synthetically despite the ability to interact with deoxyribonucleic acid (DNA) as demonstrated in circular dichroism assays. Thus, the compound does not show toxic or genotoxic activity, and therefore, it can be applied as a pigment in photovoltaic paint.

Facile one-pot synthesis and self-healing properties of tetrazole-based metallopolymers in the presence of iron salts

Self-healing MPs were prepared with tetrazole group for coordinating with FeCl3·6H2O by one-pot method. This simple and efficient synthesis will provide a green route for preparing excellent self-healing materials.

Proton exchange membrane from tetrazole-based poly (phthalazinone ether sulfone ketone) for high-temperature fuel cells

Phosphoric acid (PA)-doped proton exchange membranes (PEMs) have been prepared from tetrazole-based sulfonated poly (phthalazinone ether sulfone ketone) (AtSPPESK) for high-temperature proton exchange membrane fuel cells (HTPEMFCs). The polymer structure is characterized by fourier-transform infrared spectroscopy (FT-IR), lH nuclear magnetic resonance (1HNMR) and elemental analysis (EA). Compared with other PEMs only with tretrazole groups in side chains, this membrane with a proper PA doping capacity exhibits a much higher proton conductivity of 15 mS cm−1 at 150 °C. Both of phthalazinone groups in main chains and tetrazole groups in side chains are facial for PA uniform aggregation. To give an insight into the excellent proton conducting performance, therein, a proton transport mechanism has been proposed involving proton transport within hydrogen bonded PA molecules networks as well as acid-base interactions between tetrazole and phthalazinone groups. Meanwhile, the proper oxidative, conductivity, thermal and mechanical stability suggest that the PA doped PEM can hold as a promising membrane for HTPEMFCs.

Polyelectrolytes with tetrazole pendant groups useful in the stabilization of Au and Ag nanoparticles

ABSTRACTStabilization of metallic nanoparticles is a challenge of enormous dimensions because the nanosize nanoparticles are not stable by themselves and therefore they tend to coalesce, forming large agglomerates causing the loss of the properties of individual nanoparticles. In this work, we report the synthesis of polyelectrolytes with tetrazole groups useful as stabilizing agents of Au and Ag nanoparticles. The polyelectrolytes with tetrazole groups were synthetized from the appropriate starting materials with nitrile groups, which were successfully converted to the corresponding 1H‐tetrazole rings using 1,3‐dipolar cycloaddition with ammonium azide. These new materials were characterized by NMR and FT‐IR techniques and they were used for the stabilization of Au and Ag colloidal nanoparticles at room temperature, using sodium borohydride as reducing agent. Formation and stabilization processes of the nanoparticles were monitored by UV‐vis spectroscopy. Shape and size of nanoparticles were studied by TEM. The polyelectrolytes with tetrazole pendant group are suitable materials for synthesis and stabilization of gold nanoparticles, obtaining average sizes lower than 10 nm. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43773.

Synthesis and crystal structure of N-[(dimethylamino)methylidene]-4-[1-(4-nitrophenyl)-1H-tetrazol-5-yl]-benzenesulfonamide: Molecular docking and bioassay studies as cyclooxygenase-2 inhibitor

The synthesis of N-[(dimethylamino)methylidene]-4-[1-(4-nitrophenyl)-1H-tetrazol-5-yl]benzenesulfonamide (3) has been easily approached and the structure has been determined by X-ray crystallography. Tetrazole 3 crystallizes in the monoclinic space group C2/c, with the cell parameters determined as a = 35.5408 (18) Å, b = 7.6972 (4) Å, c = 13.0700 (7) Å3, β = 96.8598 (6)°, V = 3549.9 (3) Å3, and Z = 8. Its structure refines to R1 = 0.0341 (for 2986 observed reflections [I ≥ 2σ(I)]) and wR2 = 0.0990 (for all 3637 unique reflections). The aryl rings at the 1- and 5-positions show no conjugation to the tetrazole group, and the [(Dimethylamino)methylene]aminosulfonyl (Me2NCHNSO2) group is disordered, with the two disorder conformers being related by a pseudo mirror plane. In the crystal, intermolecular interactions between adjacent molecule of 3 are dominated by weak (2.4–2.7 Å) CeH…O and CeH…N hydrogen bonds. The molecular docking studies were carried out to understand the interaction of compound 3 within the active site of the cyclooxygenase-2 enzyme, followed by a comparison study with the celecoxib drug as a reference compound. The in vitro bioassay studies of tetrazole 3 toward cyclooxygenase-1 and cyclooxygenase-2 enzymes showed that compound 3 has no inhibition potency for either enzyme.

One–pot synthesis of ethyl‐3‐aryl‐2‐(1H‐tetrazol‐5‐yl)acrylates and 3‐(1H‐tetrazol‐5‐yl)coumarins via tandem [2+3] dipolar cycloaddition reaction‐Knoevenagel condensation

AbstractA simple, one‐pot, three‐component, two‐step tandem method has been developed for the synthesis of ethyl‐3‐aryl‐2‐(1H‐tetrazol‐5‐yl)acrylates that may have biologically importance from ethyl cyanoacetate, sodium azide and a series of aromatic aldehydes with different substituents. Reactions were performed using ammonium chloride as the catalyst and dimethylformamide as the solvent. The results indicated that electron withdrawing groups in the phenyl ring leads to comparatively more yield. When we used the salicylaldehyde precursors, the corresponding coumarin derivatives containing tetrazole group were formed in good yields. All the synthesized compounds were fully characterized by 1H, 13C NMR, FT‐IR and mass spectroscopic techniques and elemental analysis. The obtained results rationalized by proposing a suitable mechanism. Efficient and simple reaction conditions, easy isolation process and very good yields are the advantages of this strategy for the synthesis of tetrazole compounds.

α-Amino Acid-Isosteric α-Amino Tetrazoles.

The synthesis of all 20 common natural proteinogenic and 4 otherα-amino acid-isosteric α-amino tetrazoles has been accomplished, whereby the carboxyl group is replaced by the isosteric 5-tetrazolyl group. The short process involves the use of the key Ugi tetrazole reaction followed by deprotection chemistries. The tetrazole group is bioisosteric to the carboxylic acid and is widely used in medicinal chemistry and drug design. Surprisingly, several of the common α-amino acid-isosteric α-amino tetrazoles are unknown up to now. Therefore a rapid synthetic access to this compound class and non-natural derivatives is of high interest to advance the field.

Structures and photoluminescence of coordination polymers assembled from bifunctional ligand containing both tetrazole and imidazole groups

Three new coordination polymers, namely, {[Cu2(IPT)(SO4)(OH)(H2O)]·H2O}n (HIPT=5-(4-(1H-imidazol-1-yl)phenyl)- 1H-tetrazolate, 1), {[Cd2(IPT)(NPA)(OH)]·H2O}n (H2NPA=5-nitroisophthalic acid, 2), and {[Zn2(IPT)(IDC)(H2O)]·3H2O}n (H3IDC=1H-imidazole-4,5-dicarboxylic acid, 3), were assembled from a bifunctional organic ligand containing both tetrazole and imidazole groups with/without the aid of carboxylate coligands. Compound 1 possesses 2D structure built by 1D [Cu2(IPT)(SO4)(OH)]n secondary building blocks and IPT− linkers. The 2D networks are linked into 3D supramolecular framework via water chains in helical conformation. Compound 2 displays 3D pillar-layer framework with 2D layers based on tetranuclear Cd(II) SBUs and NPA2− pillars. Compound 3 exhibits a 3D framework constructed from the interconnection of 1D [Zn-IDC]n chains and binuclear Zn2(IPT)2 rings. The thermal stabilities of porous compound 3 and luminescent properties of compounds 2 and 3 have also been studied in detail. They exhibit intense solid-state fluorescent emissions at room temperature.

Rational synthesis of an exceptionally stable Zn(II) metal-organic framework for the highly selective and sensitive detection of picric acid.

Based on an organic ligand involving both carboxylate and tetrazole groups, a chemically stable Zn(II) metal-organic framework has been rationally synthesized and behaves as a fluorescence chemosensor for the highly selective and sensitive detection of picric acid, an extremely hazardous and strong explosive.

A rapidly photo-activatable light-up fluorescent nucleoside and its application in DNA base variation sensing.

A new DNA building block (d(Tet)U) bearing a tetrazole and allyloxy group at N-phenyl ring linked through an aminopropynyl linker to the 5-position of 2'-deoxyuridine was synthesized. The modified DNA can be lit up via a photoinduced intramolecular tetrazole-alkene cycloaddition reaction, but quenched when the fully-matched double strand is formed. This conspicuous difference in fluorescence could open a door for DNA single nucleotide polymorphism (SNP) typing.

Functionalization of polyacrylonitrile with tetrazole groups for ultrafiltration membranes

A series of tetrazole-functionalized polyacrylonitrile (TZ-PAN) copolymers were synthesized via a post-modification cycloaddition reaction of nitriles with azide for ultrafiltration (UF) membrane application.

Solvent-induced Keggin-based Cd(II)/Ni(II) complexes constructed from pyridyl-tetrazole: Assembly, structures and properties

Three Keggin-based CdII/NiII transition metal complexes, namely, [Cd(3-Hptz)4(CH3O)2](H3PMo12O40)·2H2O (1), [Cd(4-Hptz)4(CH3O)2](H3PMo12O40)·2H2O (2) and {[Ni3(4-ptz)2(4-Hptz)2(μ3-O)(H2O)2](HPMo12O40)}·5H2O (3) [3-ptzH=5-(3-pyridyl)-1H-tetrazole, 4-ptzH=5-(4-pyridyl)-1H-tetrazole], have been synthesized under solvothermal conditions and characterized by IR spectroscopy and single-crystal X-ray diffraction. The mixture of methanol and water was used as the solvent, which play an important role in the formation of compounds 1–3. Compounds 1 and 2 are isostructural. In 1, four 3-Hptz ligands and two methanol molecules coordinate with one CdII ion to form a [Cd(3-Hptz)4(CH3O)2] metal–organic unit, which links the adjacent discrete PMo12O403− (PMo12) anions through hydrogen bonding interactions to construct a 2D supramolecular layer. In compound 3, the tetrazole groups from one 4-Hptz and two 4-ptz ligands coordinate with three Ni ions to form a flat trinuclear subunit, which is further covered by another 4-Hptz vertically, resulting in a {[Ni3(4-ptz)2(4-Hptz)2(μ3-O)(H2O)2]2+ cluster. Adjacent trinuclear clusters connect with each other through pyridyl group of 4-ptz ligands to form a 1D chain. The PMo12 anions hang on both sides of the 1D chain, and methanol molecules may act as structure-directing agent in 3. The effect of central metals on the structures of the title compounds was discussed. In addition, the photocatalytic activities of the title complexes for the degradation of methylene blue under UV and sunlight irradiation have been investigated in detail.

Preparation and characterization of novel side-chain azobenzene polymers containing tetrazole group

A novel methacrylate monomer containing azobenzene chromophore and tetrazole moiety, 4′-(2-methacryloxyethyl)methylamino-4-(5-chlorotetrazol-1-yl)azobenzene (MACA), was synthesized and polymerized to form homopolymer (PMACA) via reversible addition-fragmentation chain transfer (RAFT) polymerization using 2-cyanoprop-2-yl dithiobenzoate (CPDB) as the RAFT agent and azobisisobutyronitrile (AIBN) as an initiator in dimethyl formamide (DMF) solution. Meanwhile, block copolymers (PMMA-b-PMACAs) were successfully obtained by RAFT polymerization of MACA using PMMA as the macro-RAFT agent and AIBN as an initiator. Gel permeation chromatography (GPC) characterization indicated that polymers with well-controlled molecular weights and narrow molecular weight distributions (Mw/Mns<1.30) were obtained. The structures of these polymers were characterized by 1H NMR and FT-IR spectra. Thermal and photoisomerization behaviors of the polymers indicated that these polymers were amorphous state with good heat stability and photoisomerization performance. Relationship between the electrochemical behavior of block copolymer (PMMA-b-PMACA) and the photoisomerization of azobenzene was investigated by cyclic voltammetry (CV) in chloroform solution, which showed that the oxidation peak of copolymer shifted from 1.0V to 0.6V during azobenzene isomerization from trans to cis form. Furthermore, surface relief gratings (SRGs) formed on the films of PMMA-b-PMACAs were also investigated with illumination of a linearly polarized Kr+ laser beam. The diffraction efficiency of the SRGs was 1.22 (PMMA-b-PMACA1), 2.38 (PMMA-b-PMACA2) and 3.02 (PMMA-b-PMACA3), respectively, which increased with the azobenzene contain for the copolymers.

Tetrazolylhydrazides as Selective Fragment‐Like Inhibitors of the JumonjiC‐Domain‐Containing Histone Demethylase KDM4A

The JumonjiC-domain-containing histone demethylase 2A (JMJD2A, KDM4A) is a key player in the epigenetic regulation of gene expression. Previous publications have shown that both elevated and lowered enzyme levels are associated with certain types of cancer, and therefore the definite role of KDM4A in oncogenesis remains elusive. To identify a novel molecular starting point with favorable physicochemical properties for the investigation of the physiological role of KDM4A, we screened a number of molecules bearing an iron-chelating moiety by using two independent assays. In this way, we were able to identify 2-(1H-tetrazol-5-yl)acetohydrazide as a novel fragment-like lead structure with low relative molecular mass (Mr =142 Da), low complexity, and an IC50 value of 46.6 μm in a formaldehyde dehydrogenase (FDH)-coupled assay and 2.4 μm in an antibody-based assay. Despite its small size, relative selectivity against two other demethylases could be demonstrated for this compound. This is the first example of a tetrazole group as a warhead in JMJD demethylases.

Docking studies and the crystal structure of two tetrazole derivatives: 5-(4-chlorophenyl)-1-{4-(methylsulfonyl)phenyl}-1H-tetrazole and 4-{5-(4-methoxyphenyl)-1H-tetrazol-1-yl}benzenesulfonamide

The structures of 5-(4-chlorophenyl)-1-{4-(methylsulfonyl)phenyl}-1H-tetrazole (3) and 4-{5-(4-methoxyphenyl)-1H-tetrazol-1-yl}benzenesulfonamide (5) have been determined by X-ray crystallography. Tetrazoles 3 and 5 crystallize in the monoclinic space groups Ia and P21/c, respectively. The cell dimensions of azole 3 are a = 11.0413 (5) Å, b = 11.8428 (5) Å, c = 12.2483 (5) Å3, β = 111.7129 (4)°, V = 1487.95 (11) Å3, and Z = 4. Its structure was refined to R1 = 0.0254 (for 3429 observed reflections [I ≥ 2σ(I)]) and wR2 = 0.0651 (for all 3300 unique reflections). The cell dimensions of azole 5 are a = 17.112 (3) Å, b = 6.5904 (10) Å, c = 12.935 (2) Å3, β = 93.1981 (19)°, V = 1456.5 (4) Å3, and Z = 4. Its structure was refined to R1 = 0.0336 (for 3010 observed reflections [I ≥ 2σ(I)]) and wR2 = 0.0875 (for all 2463 unique reflections). The tetrazole rings are essentially planar, while the aryl rings at the 1- and 5-positions of each compound show no conjugation to the tetrazole groups. Compound 5 exhibits a network of intermolecular hydrogen bonds generated by interactions between adjacent sulfonamide groups. The molecular docking studies were carried out to understand the orientation and the interaction of each molecule inside the active site of the cyclooxygenase-2 enzyme, followed by comparison with the bioassay studies as COX-2 inhibitors.

Three Candesartan Salts with Enhanced Oral Bioavailability

Three new salts, [H3N(CH2)2NH3][can]·2H2O (1), [H3N(CH2)3NH3][can]·2H2O (2), and [NH4][Hcan] (3), of the minimally soluble antihypertensive drug, Candesartan (H2can), have been prepared by solvent-assisted grinding. Salts 1–3 also have been thoroughly characterized by single-crystal X-ray diffraction, powder X-ray diffraction, Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance, thermogravimetry, and differential scanning calorimetry. In the case of 1 and 2, two protons of carboxyl and tetrazole groups of Candesartan transfer to the diamine, resulting in salts where both hydrogen bonding and electrostatic interactions that link the Candesartan and diamine (diammonium) units into a one-dimensional supramolecular ribbon. However, unlike the case in 1 and 2, only one proton from the carboxyl group of Candesartan transfers to ammonia in 3 and ionic components now assemble into a three-dimensional supramolecular network. Dissolution studies indicate that both the apparent solubility and diss...

A combined experimental and theoretical study of the tautomeric and conformational properties of (5-phenyl-tetrazol-2-yl)-acetic acid methyl ester

The tautomeric and conformational properties of a new tetrazole derivative are studied in a combined approach that includes the analysis of the experimental vibrational data together with theoretical calculation methods, especially in terms of natural bond orbital (NBO) population analysis. Moreover, the molecular and crystal structure was determined by single crystal X-ray diffraction. The compound crystallized as the 2-tautomeric form, monoclinic space group P21/c with Z=4, a=10.0630(14), b=8.2879(11), c=12.8375(18)Å, β=105.546(3)°, V=1031.5(2)Å3. The tetrazole and phenyl rings are coplanar with the acetate group oriented perpendicular to the plane. The NBO analysis showed that delocalizing interactions of the lpp(N2) lone pair orbital contributes to a strong resonance interactions with both adjacent π∗(N3N4) and π∗(N1C5) antibonding orbitals of the tetrazole group.

Synthesis of Framework Isomer MOFs Containing Zinc and 4-Tetrazolyl Benzenecarboxylic Acid via a Structure Directing Solvothermal Approach

The solvothermal synthesis of framework isomers was carried out using the hybrid carboxylate and tetrazolate functional ligand, 4-tetrazolyl benzenecarboxylic acid (H2TBC, TBC = 4-tetrazolyl benzenecarboxylate) and zinc. H2TBC was also synthesized with the solvothermal approach, and is referred herein as structure 1. Using single-crystal X-ray diffraction, we found that the tetrazolate groups of TBC show an unusual “opposite-on” coordination mode with zinc. Three previously characterized metal-organic frameworks (MOFs) were obtained by systematically changing the solvents of the H2TBC-Zn reaction, (1) ZnTBC, 2, which has a non-porous structure; (2) Zn2(TBC)2(H2O), 3, which has an amphiphilic pore structure and (3) Zn2(TBC)2{guest}, 4, which is porous and has channels containing uncoordinated N heteroatoms. Fluorescence spectra of 4 reveal a strong blue emission mainly from the TBC ligands.

Sorption Properties and Nitroaromatic Explosives Sensing Based on Two Isostructural Metal–Organic Frameworks

We first designed and synthesized a new semirigid tripodal ligand with tetrazole groups, 1,3,5-tri(4-(2H-tetrazol-5-yl)phenoxy)benzene (H3TTPB). Two isostructural microporous metal–organic frameworks (MOFs), namely [Cu3(TTPB)2(H2O)6]·5DMF (JUC-130) and [Cd3(TTPB)2(H2O)6]·6DMF (JUC-131) (JUC = Jilin University, China), were successfully synthesized under solvothermal reactions based on this ligand, which both possess two-dimensional (2D) frameworks based on similar trinuclear metal centers as secondary building units (SBUs). H3TTPB was designed as the organic building block, not only because it is suitable to construct functionalized microporous frameworks with numerous nitrogen atoms but also by reason for its blue luminescent emission. Gas sorption measurements indicated that they are both microporous frameworks. JUC-130 showed high stability in water and selective sorption capabilities for alcohol and water vapors, which may be further used for the separation of alcohol–water mixtures. In addition, JUC-131 exhibited interesting and important fluorescent properties, which can be used as one of the few known MOFs useful for the detection of nitroaromatics via “supramolecular wire effect”.