Synthesis Of Tetrazoles Research Articles

A new copper complex of lysine on mesoporous KIT-6 as a robust and homoselective catalyst in the synthesis of tetrazoles

A new copper complex of lysine on mesoporous KIT-6 as a robust and homoselective catalyst in the synthesis of tetrazoles

Synthesis of Sm‐TADDbBP@MCM‐41 as a Robust, Reusable, and Practical Nanocatalyst in the Homoselective [2 + 3] Cycloaddition Reaction

ABSTRACTSchiff‐base materials are known ligands for the coordination of metal ions and the synthesis of various stable and useful complexes. Therefore, herein, a novel Schiff‐base compound {2,2′‐((1E,11E)‐2,5,8,11‐tetra azadodeca‐1,11‐diene‐1,12‐diyl) bis (4‐bromophenol)} was introduced that formed from condensation of triethylenetetramine (TETA) and 5‐bromo‐2‐hydroxybenzaldehyde (5B2HB). This Schiff‐base ligand was labeled as TADDbBP. Besides, mesoporous MCM‐41 was synthesized using tetraethyl orthosilicate (TEOS), hydrolyzing cetyltrimethylammonium bromide (CTAB) and NaOH solution (2 M), followed by calcination at 550 °C, and further, the silanol sites on the MCM‐41's surface were modified by 3‐chloropropyltriethoxysilane (3Cl‐PTES), which modified MCM‐41 was labeled as 3‐Cl‐Pr@MCM‐41. In the next step, the synthesized TADDbBP (as Schiff‐base ligand) was grafted on 3‐Cl‐Pr@MCM‐41, which was labeled as TADDbBP@MCM‐41, and further, it was coordinated with samarium ions (which was labeled as Sm‐TADDbBP@MCM‐41 nanocatalyst) using Sm (CH3COO)3. This is the first report on the production of Sm‐TADDbBP@MCM‐41 nanocatalyst, this nanocatalyst was characterized by TEM, SEM, EDX, elemental mapping, BET method, ICP, XRD, and TGA techniques. In the final step, the catalytic performance of Sm‐TADDbBP@MCM‐41 nanocatalyst has been checked in the homo‐selective producing of tetrazoles through [2 + 3] cycloaddition of benzonitriles and sodium azide (NaN3) in PEG‐400 as available, nontoxic, green, and safe solvent. This nanocatalyst provides excellent selectivity in the synthesis of tetrazoles. In addition, Sm‐TADDbBP@MCM‐41 nanocatalyst can be separated and recycled for several cycles without significant reactivation or metal leaching.

A new Schiff-base-N-propylhydrazine-1-carbothioamide complex of copper on boehmite nanoparticles as a recoverable catalyst in the homoselective synthesis of 5-substituted tetrazoles

In this work, 2-(2-hydroxybenzylidene)hydrazine-1-carbothioamide (Schiff-base-HBHCT) was synthesized, and it was identified by FT-IR, 1H NMR, and 13C NMR spectroscopies. Besides, 3-iodopropyltrimethoxysilane (3-IPTMS) was synthesized by a simple SN2 reaction of 3-chloropropyltrimethoxysilane and potassium iodide in dry acetone. Also, boehmite nanoparticles are synthesized by a simple route and available commercial materials. Then, the surface of boehmite nanoparticles was modified by 3-IPTMS, and then it was further functionalized by Schiff-base-HBHCT. Finally, the copper ion became complex with functionalized Schiff-base-HBHCT (Cu-Schiff-base-HBHCT@boehmite). The particle size and morphology of Cu-Schiff-base-HBHCT@boehmite were studied by SEM images. Organic moieties and elemental composition of Cu-Schiff-base-HBHCT@boehmite were investigated by TGA, AAS, EDS, and WDX analysis. The surface area of Cu-Schiff-base-HBHCT@boehmite was calculated by nitrogen adsorption/desorption analysis, including BJH and BET methods. In the final step, the catalytic application of Cu-Schiff-base-HBHCT@boehmite was studied in the homoselective synthesis of tetrazoles. This catalyst has shown good reusability in the synthesis of tetrazoles.

Construction and Characterization of Magnetic Fe3O4 Nanoparticles Supported Palladium Complex: Research on Synthesis of Aryl Nitriles and Tetrazoles

Construction and Characterization of Magnetic Fe3O4 Nanoparticles Supported Palladium Complex: Research on Synthesis of Aryl Nitriles and Tetrazoles

Supported Au NPs over magnetic chitosan-gelatin nanocomposite: Investigation of its catalytic activity for one-pot synthesis of tetrazoles, study of antioxidant activity and anti-uterine cancer performances

This paper reports the synthesis of a novel class of Fe3O4@CS-Gl/Au core-shell pattern nanoparticles by employing Au NPs and chitosan-gelatin composite. The biogenic synthesis was mediated by dual composite hydrogel of chitosan and gelatin as a green reducing as well as stabilizing agent under ambient conditions. Physicochemical features the so obtained nanomaterial was assessed by using FT-IR, TEM, FE-SEM, EDX, elemental mapping, VSM and XRD. Click synthesis of 5-substituted-1H-tetrazoles utilizing aryl halides was our aim in catalytic investigation. The Fe3O4@CS-Gl/Au catalyst, which is highly effective and reusable, was used to catalyze the [3+ 2]-cycloaddition of benzonitriles with NaN3, leading to the solvent-free synthesis of corresponding tetrazole derivatives at 120 °C. This method was carried out using K4[Fe(CN)6] as a non-hazardous cyanide precursor. Following a 12-hour process, the different substrates produced yields ranging from 70 to 96%. Hot filtration, leaching and reusability studies were conducted 12 times in a succession, all of which confirmed the catalyst's resilience. Furthermore, in the biological studies % cell viability of Fe3O4@CS-Gl/Au NPs was found very low against common human uterine cell lines i.e. AN3-CA and HEC-1-A, devoid of any cytotoxicity on normal cell lines like HUVEC. The best anti-uterine effect was observed against the AN3-CA cell line. For investigating the antioxidant properties of nanobio-composite, the DPPH assay was used. Fe3O4@CS-Gl/Au NPs inhibited half of the DPPH molecules in the concentration of 139 µg/mL. The antioxidant activity of the NPs is significantly related to its anti-uterine cancer potentials. Based on the above findings, the Fe3O4@CS-Gl/Au NPs could be administered in restricting diverse human cancers.

FDU-12@AGA-Pd: A green, novel, recyclable, and highly versatile mesoporous catalyst for C[sbnd]C coupling reaction and synthesis of tetrazoles

Herein, we present an efficient, novel nanocatalyst through the immobilization of AGA-Pd onto the inside of mesoporous silica FDU-12 channels that were successfully synthesized by a simple procedure. The catalytic activity of FDU-12@AGA-Pd was investigated for the synthesis of 1H-tetrazole derivatives and the Suzuki reaction. The synthesized compounds were identified and confirmed with the help of 1H-NMR. In this research, the nanocatalyst was prepared by the immobilization of palladium into FDU-12 channels coated with 2-amino-5-guanidinovaleric acid (AGA). N2 adsorption-desorption isotherms indicated excellent BET surface area for FDU-12 and FDU-12@AGA-Pd, which is 627.27 and 106.69 (m2 /g), respectively. The physical and chemical properties of raw and modified samples (FDU-12, FDU-12@AGA-Pd) were characterized by Thermogravimetric analysis (TGA), N2 adsorption-desorption analysis, Inductively coupled plasma optical emission spectroscopy (ICP-OES), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Fourier transforms infrared spectroscopy (FT-IR), Mapping, and X-ray diffraction (XRD). The synthesized mesoporous nanocatalyst was recovered and reused in five continuous cycles without considerable change in its catalytic activity.SynopsisOur findings will help researchers and industrial factories to apply a green and sustainable mesoporous catalyst to produce a variety of valuable organic compounds and pharmaceutical products.

Catalytic Tetrazole Synthesis via [3+2] Cycloaddition of NaN3 to Organonitriles Promoted by Co(II)-complex: Isolation and Characterization of a Co(II)-diazido Intermediate.

The [3+2] cycloaddition of sodium azide to nitriles to give 5-substituted 1H-tetrazoles is efficiently catalyzed by a Cobalt(II) complex (1) with a tetradentate ligand N,N-bis(pyridin-2-ylmethyl)quinolin-8-amine. Detailed mechanistic investigation shows the intermediacy of the cobalt(II) diazido complex (2), which has been isolated and structurally characterized. Complex 2 also shows good catalytic activity for the synthesis of 5-substituted 1H-tetrazoles. These are the first examples of cobalt complexes used for the [3+2] cycloaddition reaction for the synthesis of 1H-tetrazoles under homogeneous conditions.

Innovative synthesis of drug-like molecules using tetrazole as core building blocks.

Tetrazole is widely utilized as a bioisostere for carboxylic acid in the field of medicinal chemistry and drug development, enhancing the drug-like characteristics of various molecules. Typically, tetrazoles are introduced from their nitrile precursors through late-stage functionalization. In this work, we propose a novel strategy involving the use of diversely protected, unprecedented tetrazole aldehydes as building blocks. This approach facilitates the incorporation of the tetrazole group into multicomponent reactions or other chemistries, aiding in the creation of a variety of complex, drug-like molecules. These innovative tetrazole building blocks are efficiently and directly synthesized using a Passerini three-component reaction (PT-3CR), employing cost-effective and readily available materials. We further showcase the versatility of these new tetrazole building blocks by integrating the tetrazole moiety into various multicomponent reactions (MCRs), which are already significantly employed in drug discovery. This technique represents a unique and complementary method to existing tetrazole synthesis processes. It aims to meet the growing demand for tetrazole-based compound libraries and novel scaffolds, which are challenging to synthesize through other methods.

The synthesis of biochar from biomass waste recycling and its surface modification for immobilization of a new Cu complex as a reusable nanocatalyst in the homoselective synthesis of tetrazoles

The synthesis of biochar from biomass waste recycling and its surface modification for immobilization of a new Cu complex as a reusable nanocatalyst in the homoselective synthesis of tetrazoles

Humic Acid: A Promising and Green Bioorganic Catalyst in Organic Syntheses

AbstractThe growing pollution and threat to the environment demand green synthetic methods. Green chemistry mainly focuses on minimizing the waste and utilization of green solvents, energy sources, and catalysts and prefers one‐pot reactions. In this context, humic acid (HA), a natural bioorganic catalyst found in rivers, peat coal and sewage; is a high molecular weight macromolecule containing multifunctional groups, mainly contains quinone, phenolic OH, and COOH groups which make it acidic and activate carbonyl groups by protonation. Owing to its green aspect such as biodegradability, recyclability and reusability, humic acid is considered as sustainable bioorganic catalyst which meets the criteria for industrial requirements. The HA is mild acidic in nature, thus many functional groups tolerate in the HA catalyzed reactions. After few initial reports in 2001 and 2009, the HA catalyzed reactions gained much attention by the organic synthetic community from 2019 in aldol condensation, Knoevenagel condensation, Claisen‐Schmidt reaction, Michael addition, Strecker synthesis, tetrazole synthesis, Hantzsch dihydropyridine synthesis, hydrosilylation of terminal alkenes, hydrogenation, α‐aminophosphonate synthesis, cross coupling reactions such as Heck and Suzuki coupling reactions. Herein we report the comprehensive analysis on the role of HA in organic transformations providing diverse array of molecular scaffolds till date and future perspective.

Three components: one-pot synthesis of tetrazoles using silica-supported melamine tri-sulfonic acid, an efficient and reusable heterogeneous catalyst

The effective and straightforward procedure for synthesizing 1-H 1,2,3,4 tetrazole involves the reaction of a primary amine, triethyl orthoformate and sodium azide in the presence of silica-supported melamine tri sulfonic acid. One pot synthesis of tetrazole derivatives over the silica-supported melamine tri sulfonic acid catalyst reveals that the existence of strong acid sites in silica makes it more efficient with respect to the shortening of the reaction time (5–6 h) and excellent yield (75-84%) as compared to the other catalysts. This process includes benefits like a more environmentally friendly path, an easier work-up, a reusable catalyst and a high yield.

Green Methodologies for Tetrazole Synthesis from Different Starting Materials: A Recent Update

Abstract: Tetrazole is a most versatile pharmacophore of which more than twenty FDAapproved drugs have been marketed globally for the management of various diseases. In spite of many remarkable and consistent efforts having been made by the chemists towards the development of greener and sustainable strategies for the synthesis of tetrazole derivatives, this approach still needs more attention. The present review focuses on the green synthetic approach for the preparation of tetrazole derivatives from different starting materials such as nitrile, isonitrile, carbonyl, amine, amide, oxime and terminal alkyne functions. The mechanism of tetrazole synthesis from different substrates is discussed. In addition to this, a four component Ugi-azide reaction to the tetrazole synthesis is also described. Of note, the present articles exploited several water-mediated and solvent-free methodologies for tetrazole synthesis. The important key features of tetrazole synthesis were pinpointing in each synthetic scheme which provides excellent guide to those searching for selective procedure to achieve the desired transformation. This review seeks to present a timely account (2011-2023) on the splendid array of ecofriendly procedures of synthesis known today for the preparation of tetrazole derivatives from different starting materials. The rational of this review is to enlighten recent advancements in the synthesis of tetrazole derivatives from different substrates.

A new Schiff base 2-benzoylpyridine-based copper complex on boehmite nanoparticles as a recoverable nanocatalyst for the homoselective synthesis of 5-substituted tetrazoles.

In this study, boehmite nanoparticles (B-NPs) were prepared by a simple process and then their surface was modified by (3-aminopropyl)triethoxysilane (3-APTES). The modified B-NPs (3-APTES@B-NPs) were functionalized by 2-benzoylpyridine Schiff-base ligand toward the immobilization of the Schiff-base 2-benzoylpyridine ligand on the 3-APTES@B-NPs's surface (2BP-Schiff-base@B-NPs). Finally, copper ions were coordinated with the supported Schiff-base ligand on B-NPs toward the formation of the final catalyst (Cu-2BP-Schiff-base@B-NPs). The prepared Cu-2BP-Schiff-base@B-NPs were characterized using FT-IR spectroscopy, BET analysis, XRD, SEM, AAS, TGA, EDX and elemental mapping. Further, Cu-2BP-Schiff-base@B-NPs were applied as a homoselective and recyclable catalyst for the synthesis of a diverse range of 5-substituted tetrazoles in PEG-400 as a green solvent. The main benefits of this protocol are high homoselectivity attributes, short reaction times, high product yields and TOF values, and further addition to the catalyst ability to be recycled at least four times without significantly losing catalytic efficiency.

Eco-friendly and sustainable basil seed hydrogel-loaded copper hydroxide-based catalyst for the synthesis of propargylamines and tetrazoles.

The broad use of propargyl amines and tetrazoles in pharmaceutical applications presents a well-established challenge. Their synthesis relies heavily on catalysis, which, in turn, has been hindered by the scarcity of stable and practical catalysts. In response to this issue, we have developed an environmentally friendly and sustainable catalyst by infusing copper hydroxide into basil seed hydrogel (Cu(OH)2-BSH), creating a 3D nanoreactor support structure. To verify the structural, physical, chemical, and morphological properties of the prepared samples, a comprehensive analysis using various techniques, including FT-IR, EDX, FE-SEM, TEM, XRD, BET, TGA, and XPS, were conducted. The results not only confirmed the presence of Cu(OH)2 but also revealed a porous structure, facilitating faster diffusion and providing a substantial number of active sites. This catalyst boasts a high surface area and can be easily recovered, making it a cost-effective, safe, and readily available option. This catalyst was applied to the synthesis of propargyl amines and tetrazoles through multi-component reactions (MCRs), achieving excellent results under mild conditions and in a remarkably short timeframe. Consequently, this work offers a straightforward and practical approach for designing and synthesizing metal hydroxides and 3D hydrogels for use in heterogeneous catalysis during organic syntheses. This can be achieved using basic and affordable starting materials at the molecular level.

A novel Cu complex coated on hercynite magnetic nanoparticles as an efficient and recoverable nanocatalyst for the selective synthesis of tetrazoles

A novel Cu complex coated on hercynite magnetic nanoparticles as an efficient and recoverable nanocatalyst for the selective synthesis of tetrazoles

A new neodymium complex on renewable magnetic biochar nanoparticles as an environmentally friendly, recyclable and efficient nanocatalyst in the homoselective synthesis of tetrazoles.

Inexpensive, stable, selective, and recyclable nanocatalysts, waste regeneration, and utilization of safe and available solvents are of interest and important factors in laboratory science and industrial applications of green chemistry. Therefore, herein, biochar nanoparticles (BNPs) were synthesized through chicken manure pyrolysis as a novel method for waste recycling. Then, in order to improve their recyclability, the obtained BNPs were magnetized using magnetic nickel nanoparticles. Then, the surface of the biochar magnetic nanoparticles (BMNPs) was modified by (3-chloropropyl)trimethoxysilane (3-CPTMS) and further a novel neodymium Schiff-base complex was immobilized on the surface of the modified BMNPs, denoted as Nd-Schiff-base@BMNPs. The obtained supported neodymium complex was used as a practical, selective, biocompatible, commercial, and reusable heterogeneous nanocatalyst. The biochar support of this nanocatalyst was formed from pyrolysis of chicken manure; therefore, it is cheap, economically viable, green and also compatible with the principles of green chemistry. Nd-Schiff-base@BMNPs acts selectively in organic reactions and also it can easily be recovered using an external magnet and reused, which is compatible with the principles of green chemistry. This nanocatalyst was characterized by wavelength-dispersive X-ray spectroscopy (WDX), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma (ICP), and N2 adsorption-desorption (BET method) techniques. In the next step, the catalytic utilization of Nd-Schiff-base@BMNPs was investigated in the homoselective synthesis of 5-substituted 1H-tetrazole compounds from [3 + 2] cycloaddition of sodium azide (NaN3) and organo-nitriles in PEG-400 as a green solvent. Utilizing PEG-400 as a solvent offers various advantages, e.g. cheap, readily available, and environmentally friendly solvent as well as rapid separation and high purity of products. Therefore, this work is fully compatible with the principles of green chemistry.

Synthesis of a Novel Nanomagnetic N4 Bis Schiff Base Complex of Copper (II) As an Efficient Catalyst for Click Synthesis of Tetrazoles

Synthesis of a Novel Nanomagnetic N4 Bis Schiff Base Complex of Copper (II) As an Efficient Catalyst for Click Synthesis of Tetrazoles

Homoselective Synthesis of tetrazoles and chemoselective oxidation of sulfides using Ni(II)-Schiff base complex stabilized on 3-dimensional mesoporous KIT-6 surface as a recyclable nanocatalyst

Mesoporous silica with thick expanded walls, open porosity, and excellent thermal stability is a relatively new structure known as KIT-6. In this study, KIT-6 mesoporous was synthesized by using pluronic surfactant P123 as a modulator in an acidic environment. The synthesized KIT-6 was then modified by 3-chloropropyltrimethoxysilane (3-CPTMS) and finally, the nickel metal complex was fixed on the modified mesoporous KIT-6. IR, BET, XRD, EDS, SEM, AAS, and TGA methods were employed to examine the as-prepared catalyst. The proposed catalyst was then used for selective sulfides oxidation and preparation of tetrazole derivatives. The synthesized catalyst was found to be efficient and practical as it produced organic compounds in proper TOF and TON amounts, demonstrating the catalyst's practicality and efficiency.

The new Schiff‐base complex of copper(II) grafted on mesoporous KIT‐6 as an effective nanostructure catalyst for the homoselective synthesis of various tetrazoles

In this work, KIT‐6 mesoporous silica material was used to create heterogeneous catalyst due to its excellent surface area, substantial pore volume, and highly functionalized surface. A copper(II) Schiff‐base complex was fabricated on the surface of KIT‐6. For this purpose, (3‐iodopropyl)trimethoxysilane (IPTMS) was synthesized as a linker from (3‐choloropropyl)trimethoxysilane through a simple SN2 reaction using NaI. On the other hand, ligand (a) was synthesized from condensation of diethylenetriamine (DETA) and salicylaldehyde (SA), which was identified by IR and 1H‐NMR techniques. In order to, prepare Sal(PMeOSi)DETA (b), ligand (a) was reacted with IPTMS. One of the challenges of this synthesis was to prove the linkage between the ligand (a) and the IPTMS, which was proved by 1H‐NMR technique. In the next step, the Schiff base complex of copper(Cu(II)[Sal(PMeOSi)DETA]) (c) was synthesized using a complexation reaction of Cu(NO3)2.3 H2O and b. Finally, the obtained copper complex was fixed on KIT‐6, {Cu(II)[Sal(PMeOSi)DETA]} as the new reusable and practical catalyst. This catalyst has been identified using IR, BET, EDS, XRD, SEM, and TGA methods and employed in the synthesis of different tetrazoles for the first time. All tetrazoles were prepared with high yields, and good TOF and TON values, indicating excellent catalytic performance. This catalyst shows excellent homoselectivity in the synthesis of five‐substituted 1H‐tetrazoles. Also, it can be recovered and reused several times without a significant decrease in its catalytic activity or copper leaching.

Synthesis and characterization of a new Schiff-base complex of copper on magnetic MCM-41 nanoparticles as efficient and reusable nanocatalyst in the synthesis of tetrazoles

In this work, first we synthesized 2,2′-((1Z,11Z)-2,5,8,11-tetraazadodeca-1,11-diene-1,12-diyl)bis(4-bromophenol) (TDBB) as a new Schiff-base ligand. Also, magnetic MCM-41 nanoparticles (MCM-41/Fe3O4) were synthesized by doping Fe3O4 into mesoporous MCM-41 channels. Then, MCM-41/Fe3O4 nanoparticles were modified by TDBB. Finally, a copper Schiff-base complex of TDBB (Cu-TDBB@MCM-41/Fe3O4 was synthesized by anchoring copper ions on the modified MCM-41/Fe3O4. The prepared nanocatalyst has been characterized by various techniques such as SEM, EDS, AAS, WDX, TGA, and XRD. Cu-TDBB@MCM-41/Fe3O4 nanoparticles were employed as an environmentally friendly, valuable, and reusable nanocatalyst for the synthesis of 5-substituted 1H-tetrazoles and all products were formed with good to excellent yields. In addition, Cu-TDBB@MCM-41/Fe3O4 nanocatalyst can be recovered and reused up to six times without considerably decreasing catalytic efficiency or metal leaching.