Design, synthesis and application of a magnetic H-bond catalyst in the preparation of new nicotinonitriles via cooperative vinylogous anomeric-based oxidation.

Herein, we designed and synthesized a new H-bond magnetic catalyst with 2-tosyl-N-(3-(triethoxysilyl)propyl)hydrazine-1-carboxamide as a sensitive H-bond donor/acceptor. We created an organic structure with a urea moiety on the magnetic nanoparticles, which can function as a hydrogen bond catalyst. Hydrogen bond catalysts serve as multi-donor/-acceptor sites. Additionally, we utilized magnetic nanoparticles in the production of the target catalyst, giving it the ability to be recycled and easily separated from the reaction medium with an external magnet. We evaluated the catalytic application of Fe3O4@SiO2@tosyl-carboxamide as a new magnetic H-bond catalyst in the synthesis of new nicotinonitrile compounds through a multicomponent reaction under solvent-free and green conditions with high yields (50-73%). We confirmed the structure of Fe3O4@SiO2@tosyl-carboxamide using various techniques. In addition, the structures of the desired nicotinonitriles were confirmed using melting point, 1H-NMR, 13C-NMR and HR-mass spectrometry analysis. The final step of the reaction mechanism was preceded via cooperative vinylogous anomeric-based oxidation (CVABO).

Synthesis and Application of Task-Specific Bimetal-Organic Frameworks in the Synthesis of Biological Active Spiro-Oxindoles.

The use of click chemistry as a smart and suitable method for the development of new heterogeneous catalysts is based on metal-organic frameworks as well as the production of organic compounds. The development of the click chemistry method can provide a new strategy to achieve superior properties of MOFs. Here, the two metals Co and Fe are used to create a bimetallic-organic framework. In the following, the click chemistry and postmodification method are well organized and an acidic heterogeneous porous catalyst is developed. This prepared catalyst was used as a highly efficient catalyst for the preparation of new spiro-oxindoles obtained through click chemistry with good to excellent yields (80-94%). This presented catalytic system can compete with the best reported catalytic systems. The findings showed that the presence of Co and Fe metals in the MOF, and the presence of the triazole ring on the catalyst, can increase the catalytic efficiencies. This study offers novel insights into the architecture of Metal-Organic Frameworks (MOFs), click chemistry, and biologically active compounds. Additionally, the research explores the antibacterial properties of the synthesized spiro-oxindoles and catalysts. The findings reveal significant antibacterial activities of the synthesized compounds against S. aureus, MRSA, and E. coli bacteria.

Urea-rich porous organic polymer as a hydrogen bond catalyst for Knoevenagel condensation reaction and synthesis of 2,3-dihydroquinazolin-4(1H)-ones.

In this research, a new urea-rich porous organic polymer (urea-rich POP) as a hydrogen bond catalyst was synthesized via a solvothermal method. The physiochemical properties of the synthesized urea-rich POP were investigated by using different analyses like Fourier transform infrared (FT-IR) spectroscopy, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), derivative thermogravimetry (DTG), energy-dispersive X-ray spectroscopy (EDS), elemental mapping analysis, X-ray diffraction analysis (XRD) and Brunauer-Emmett-Teller (BET) techniques. The preparation of urea-rich POP provides an efficacious platform for designing unique hydrogen bond catalytic systems. Accordingly, urea-rich POP, due to the existence of several urea moieties as hydrogen bond sites, has excellent performance as a catalyst for the Knoevenagel condensation reaction and multi-component synthesis of 2,3-dihydroquinazolin-4(1H)-ones.

Application of Functionalized Zn-Based Metal-Organic Frameworks (Zn-MOFs) with CuO in Heterocycle Synthesis via Azide-Alkyne Cycloaddition.

The main goal of this article is to discuss the expansion of click chemistry. A new catalyst composed of CuO nanoparticles embedded in Zn-MOF with the ligand 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine (H3L) is presented. The incorporation of CuO nanoparticles into the Zn-MOF structure led to desirable morphology and catalytic properties. The designed catalyst was evaluated for its catalytic role in the multicomponent reaction and copper-catalyzed azide-alkyne cycloaddition (CuAAC) for preparation of triazole rings with 80-91% yield. The catalyst demonstrated an appealing architecture and exhibited robustness, high efficiency, and environmental friendliness. Characterization of the catalyst was performed using various techniques, including Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopes (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDX), elemental mapping, and X-ray diffraction (XRD). The results suggest that this novel catalyst has the potential to be a valuable tool in the development of new synthetic approaches for a wide range of applications.

Catalytic Application of Functionalized Bimetallic-Organic Frameworks with Phosphorous Acid Tags in the Synthesis of Pyrazolo[4,3-e]pyridines.

Combining two different metals for the synthesis of a metal-organic framework (MOF) is a smart strategy for the architecture of new porous materials. Herein, a bimetal-organic framework (bimetal-MOFs) based on Fe and Co metals was synthesized. Then, phosphorous acid tags were decorated on bimetal-MOFs via a postmodification method as a new porous acidic functionalized catalyst. This catalyst was used for the synthesis of pyrazolo[4,3-e]pyridine derivatives as suitable drug candidates. The present study provides new insights into the architecture of novel porous heterogeneous catalysts based on a bimetal-organic framework (bimetal-MOFs). The type of final structures of catalyst and pyrazolo[4,3-e]pyridine derivatives were determined using different techniques such as fourier transform infrared (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), SEM-elemental mapping, N2 adsorption-desorption isotherm, Barrett-Joyner-Halenda (BJH), thermogravimetry/differential thermal analysis (TG/DTA), 1H NMR, and 13C NMR.

Synthesis of picolinates via a cooperative vinylogous anomeric-based oxidation using UiO-66(Zr)-N(CH2PO3H2)2 as a catalyst.

The anomeric effect highlights the significant influence of the functional group and reaction conditions on oxidation-reduction. This article successfully investigates the anomeric effect in the synthesis of picolinate and picolinic acid derivatives through a multi-component reaction involving 2-oxopropanoic acid or ethyl 2-oxopropanoate, ammonium acetate, malononitrile, and various aldehydes. To facilitate this process, we employed UiO-66(Zr)-N(CH2PO3H2)2 as a novel nanoporous heterogeneous catalyst. The inclusion of phosphorous acid tags on the UiO-66(Zr)-N(CH2PO3H2)2 offers the potential for synthesizing picolinates at ambient temperature.

Synthesis of new hybrid pyridines catalyzed by Fe3O4@SiO2@urea-riched ligand/Ch-Cl.

Herein, a new heterogeneous catalytic system through modification of urea functionalized magnetic nanoparticles with choline chloride [Fe3O4@SiO2@urea-riched ligand/Ch-Cl] was designed and synthesized. Then, the synthesized Fe3O4@SiO2@urea-riched ligand/Ch-Cl was characterized by using FT-IR spectroscopy, FESEM, TEM, EDS-Mapping, TGA/DTG and VSM techniques. After that, the catalytic usage of Fe3O4@SiO2@urea-riched ligand/Ch-Cl was investigated for the synthesis of hybrid pyridines with sulfonate and/or indole moieties. Delightfully, the outcome was satisfactory and the applied strategy represents several advantages such as short reaction times, convenience of operation and relatively good yields of obtained products. Moreover, the catalytic behavior of several formal homogeneous DESs was investigated for the synthesis of target product. In addition, a cooperative vinylogous anomeric-based oxidation pathway was suggested as rational mechanism for the synthesis of new hybrid pyridines.

Application of Zr-MOFs based copper complex in synthesis of pyrazolo[3, 4-b]pyridine-5-carbonitriles via anomeric-based oxidation.

In this research article, Zr-MOFs based copper complex as a novel heterogeneous and porous catalyst was designed and prepared. The structure of catalyst has verified by various techniques such as FT-IR, XRD, SEM, N2 adsorption-desorption isotherms (BET), EDS, SEM-elemental mapping, TG and DTG analysis. UiO-66-NH2/TCT/2-amino-Py@Cu(OAc)2 was used as an efficient catalyst in the synthesis of pyrazolo[3,4-b]pyridine-5-carbonitrile derivatives. The aromatization of titled molecules is performed via a cooperative vinylogous anomeric-based oxidation both under air and inert atmospheres. The unique properties of the presented method are short reaction time, high yield, reusability of catalyst, synthesis of desired product under mild and green condition.

Application of Metal-Organic Frameworks with Sulfonic Acid Tags in the Synthesis of Pyrazolo[3,4-b]pyridines via a Cooperative Vinylogous Anomeric-Based Oxidation.

Herein, we report the design and synthesis of Co-MOF-71/imidazole/SO3H as a novel porous catalyst with sulfonic acid tags. The structure and morphology of the catalyst were investigated using various techniques such as Fourier transform-infrared spectroscopy (FT-IR), X-ray diffraction, scanning electron microscopy (SEM), SEM elemental mapping, energy-dispersive X-ray spectroscopy, Barret-Joyner-Halenda, and N2 adsorption-desorption isotherms. Co-MOF-71/imidazole/SO3H was studied in the preparation of novel pyrazolo[3,4-b]pyridines under mild and green conditions via a cooperative vinylogous anomeric-based oxidation. A wide range of mono and bis pyrazolo[3,4-b]pyridines were synthesized with good to excellent yields (65-82%). A hot filtration test for the heterogeneous nature of the catalyst indicated the high stability of the prepared catalyst. The recyclability of Co-MOF-71/imidazole/SO3H is another advantage of the present methodology. The structures of the final products were confirmed using FT-IR, 1H-NMR, and 13C-NMR spectroscopic techniques.

Application of Nanomagnetic Metal-Organic Frameworks in the Green Synthesis of Nicotinonitriles via Cooperative Vinylogous Anomeric-Based Oxidation.

In the current study, we synthesized a new nanomagnetic metal-organic framework Fe3O4@MIL-53(Al)-N(CH2PO3)2 and characterized it using various techniques. This nanomagnetic metal-organic framework was used for the synthesis of a wide range of nicotinonitrile derivatives as suitable drug candidates by a four-component reaction of 3-oxo-3-phenylpropanenitrile or 3-(4-chlorophenyl)-3-oxopropanenitrile, ammonium acetate (NH4OAc), acetophenone derivatives, and various aldehydes including those bearing electron-donating, electron-withdrawing, and halogen groups, which afforded desired products (27 samples) via a cooperative vinylogous anomeric-based oxidation (CVABO) mechanism under solvent-free conditions in excellent yields (68-90%) and short reaction times (40-60 min). Increasing the surface-to-volume ratio, easy separation of the catalyst using an external magnet, and high chemical and temperature stability are the advantages of the described nanomagnetic metal-organic frameworks.

A comparative study on the design and application of new nano benzimidazolium gemini ionic liquids for curing interfacial properties of the crude oil-water system.

Gemini surface active ionic liquids (GSAILs) are considered a new prosperous class of ionic liquids and recognized as high performance materials. The present study explores the capabilities of the newly synthesized GSAILs, constructed from two benzimidazole rings attached via a four or a six carbon spacer, namely [C4benzim-Cn-benzimC4][Br2], n = 4 and 6. The products were characterized with FT-IR, NMR, XRD, TGA, DTG and SEM methods and were used in curing interfacial properties of the crude oil-water system. The interfacial tension (IFT) was reduced to about 64 and 71% under critical micelle concentrations (CMCs) of 0.028 and 0.025 mol dm-3 at 298.2 K for n = 4 and 6 GSAILs, respectively. Temperature significantly assisted this effect. Both the GSAILs could transfer the wettability of the solid surface from oil-wet to water-wet. Further, stable oil/water emulsions were produced, having emulsion indices of 74.2 and 77.3% for n = 4 and 6 GSAILs, respectively. Compared to homologous imidazolium GSAILs, the benzimidazolium products revealed better performance in the sense of exhibiting desired effects on the investigated interfacial properties. These can be attributed to the stronger hydrophobicity of the benzimidazolium rings as well as better spreading of the molecular charges. The Frumkin isotherm could exactly reproduce the IFT data, leading to precise determination of the important adsorption and thermodynamic parameters.

Acidic tributyl phosphonium-based ionic liquid: an efficient catalyst for preparation of diverse pyridine systems via a cooperative vinylogous anomeric-based oxidation.

In this study, an acidic phosphonium-based ionic liquid, namely tributyl(3-sulfopropyl)phosphonium trifluoroacetate, was designed and synthesized via a facile and green route. From an accurate perspective, the structure of the prepared ionic liquid was investigated using FT-IR, 1H NMR and 13C NMR spectroscopies, and EDX, elemental mapping and TGA/DTG analysis. In this intensive research, catalytic application of tributyl(3-sulfopropyl)phosphonium trifluoroacetate was explored for the preparation of diverse pyridine systems such as triaryl pyridines, 2-amino-3-cyanopyridines and indolyl pyridines via a cooperative vinylogous anomeric-based oxidation (CVABO). The observed results proved that prepared acidic phosphonium-based ionic liquid is a effective catalyst for the multicomponent synthesis of pyridines.

A convenient catalytic method for preparation of new tetrahydropyrido[2,3-d]pyrimidines via a cooperative vinylogous anomeric based oxidation.

In this study, a novel functionalized metal-organic frameworks MIL-125(Ti)-N(CH2PO3H2)2 was designed and synthesized via post-modification methodology. Then, MIL-125(Ti)-N(CH2PO3H2)2 as a mesoporous catalyst was applied for the synthesis of a wide range of novel tetrahydropyrido[2,3-d]pyrimidines as bioactive candidate compounds by one-pot condensation reaction of 3-(1-methyl-1H-pyrrol-2-yl)-3-oxopropanenitrile, 6-amino-1,3-dimethylpyrimidine-2,4(1H,3H)-dione and aromatic aldehydes at 100 °C under solvent-free condition. Interestingly, the preparation of tetrahydropyrido[2,3-d]pyrimidine was achieved via vinylogous anomeric based oxidation mechanism with a high yield and short reaction time.

Phosphonic acid tagged carbon quantum dots encapsulated in SBA-15 as a novel catalyst for the preparation of N-heterocycles with pyrazolo, barbituric acid and indole moieties.

Herein, we have presented a new insight for the synthesis of a hybrid heterogeneous catalyst. For this purpose, phosphonic acid tagged carbon quantum dots of CQDs-N(CH2PO3H2)2 encapsulated and assembled in channels of SBA-15 using a post-modification strategy. The mesoporous catalyst of functionalized carbon quantum dots (CQDs) was characterized by several techniques. CQDs-N(CH2PO3H2)2/SBA-15 as an excellent catalyst was applied for the preparation of novel pyrazolo[4',3':5,6]pyrido[2,3-d]pyrimidine derivatives by using pyrazole, barbituric acid and indole moieties at 100 °C under the solvent-free condition. The present work shows that a significant increase in the catalytic activity can be achieved by a rational design of mesoporous SBA-15 modified with CQDs for the synthesis of biological active candidates. The synthesized compounds did not convert to their corresponding pyridines via an anomeric-based oxidation mechanism.

Synthesis of pyrimidine-6-carbonitriles, pyrimidin-5-ones, and tetrahydroquinoline-3-carbonitriles by new superb oxovanadium(V)-[5,10,15,20-tetrakis(pyridinium)-porphyrinato]-tetra(tricyanomethanide) catalyst via anomeric based oxidation.

Oxovanadium(V)-[5,10,15,20-tetrakis(pyridinium)-porphyrinato]-tetra(tricyanomethanide) [(VO)TPP][(TCM)4] was designed, synthesized and characterized by various techniques such as FT-IR, EDX, SEM equipped with EDX mappings, CHN elemental analysis, ICP-OES, XRD, SEM, TEM, TGA, DTA, DRS, Kubelka-Munk function (Tauc's plot), and UV-Vis analyses. Then, [(VO)TPP][(TCM)4] was used as a benign and expedient catalyst for the synthesis of numerous heterocyclic compounds such as 5-amino-7-(aryl)-4,7-dihydro-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitriles, 5-amino-7-(aryl)-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitriles, 7-(aryl)-7,12-dihydro-5H-isochromeno[4,3-d][1,2,4]triazolo[1,5-a]pyrimidin-5-ones, and 4-(aryl)-2-(1H-indol-3-yl)-5,6,7,8-tetrahydroquinoline-3-carbonitriles under solvent-free conditions at 100 °C via a cooperative geminal-vinylogous anomeric based oxidation.

Retraction: Synthesis and characterization of novel silica-coated magnetic nanoparticles with tags of ionic liquid. Application in the synthesis of polyhydroquinolines.

[This retracts the article DOI: 10.1039/C5RA23670C.].

Retraction: Experimental and theoretical studies of the nanostructured {Fe3O4@SiO2@(CH2)3Im}C(CN)3 catalyst for 2-amino-3-cyanopyridine preparation via an anomeric based oxidation.

[This retracts the article DOI: 10.1039/C6RA12299J.].

Retraction: Design of 1-methylimidazolium tricyanomethanide as the first nanostructured molten salt and its catalytic application in the condensation reaction of various aromatic aldehydes, amides and ß-naphthol compared with tin dioxide nanoparticles.

[This retracts the article DOI: 10.1039/C5RA02718G.].

Catalytic synthesis of new pyrazolo [3,4-b] pyridine via a cooperative vinylogous anomeric-based oxidation.

In this study, a novel nano-magnetic metal-organic frameworks based on Fe3O4 namely Fe3O4@MIL-101(Cr)-N(CH2PO3)2 was synthesized and fully characterized. The prepared sample was used as catalyst in the synthesis of pyrazolo [3,4-b] pyridines as convenient medicine by condensation reaction of aldehydes, 5-(1H-Indol-3-yl)- 2H-pyrazol-3-ylamine and 3-(cyanoacetyl)indole via a CVABO. The products were obtained with high yields at 100 °C and under solvent-free conditions.

Synthesis and application of novel urea-benzoic acid functionalized magnetic nanoparticles for the synthesis of 2,3-disubstituted thiazolidin-4-ones and hexahydroquinolines.

In this work, we reported the synthesis and application of a new urea-benzoic acid containing ligand [(OEt)3Si(CH2)3-urea-benzoic acid] for the functionalization of silica coated magnetic nanoparticles. The resulting structure, namely Fe3O4@SiO2@(CH2)3-urea-benzoic acid, was characterized through different techniques including FT-IR, SEM, EDX-Mapping, VSM and TGA/DTG analysis. Then, Fe3O4@SiO2@(CH2)3-urea-benzoic acid was applied as a heterogeneous dual acidic and hydrogen bonding catalyst for the synthesis of 2,3-disubstituted thiazolidin-4-ones and hexahydroquinolines under mild and green reaction conditions. More importantly, all of the desired products were obtained with relatively good yields. Also, the catalyst was recovered and reused for four successive runs without significant reduction in yield of the model reaction.