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The new type of the four‐component tandem Knoevenagel–Michael reaction was discovered: the transformation of arylaldehydes, N,N′‐dimethylbarbituric acid, malononitrile, and morpholine in alcohols and other organic solvents without any other additives at ambient temperature resulted in the selective formation of a new substituted unsymmetrical ionic scaffold with two pharmacology‐active heterocyclic rings. This new four‐component reaction is a simple and efficient route to a previously unknown substituted ionic unsymmetrical scaffold containing N,N′‐dimethylbarbituric acid and morpholine. These ionic scaffolds are promising for various biomedical applications, for example, as anticonvulsants and anti‐inflammatory drugs, as well as anti‐AIDS agents. In this research, we also accomplished the efficient cyclization of morpholin‐4‐ium 5‐(2,2‐dicya‐no‐1‐arylethyl)‐1,3‐dimethyl‐2,6‐di‐oxo‐1,2,3,6‐tetrahydro‐pyrimidin‐4‐olates by the action of NBS–NaOAc system, with the formation of 5,7‐dimethyl‐4,6,8‐trioxo‐2‐aryl‐5,7‐diazaspiro[2.5]octane‐1,1‐dicarbonitriles in 83%–98% yields. In the final stage of our research, direct one‐pot multicomponent transformation of benzaldehydes, N,N′‐dimethylbarbituric acid, and malononitrile into spirobarbituric cyclopropanes was accomplished in 75%–97% yields. The spiro‐barbituric cyclopropanes are potentially active as remedies against various inflammatory, infectious, immunological, or malignant diseases. [ABSTRACT FROM AUTHOR]

This study reveals that the synthesis of a novel heterogeneous gaur gum-supported DABCO functionalized nickel(II)catalyst and its application for the synthesis of 2-amino-3-cyano-7-hydroxy-4H-chromenes. The synthesized GG@Ni(II) catalyst was characterized by FT-IR, XRD, EDX, and SEM techniques. The catalytic activities of this synthesized heterogeneous catalyst were examined in one-pot multicomponent synthesis of chromene derivatives under ultrasonic condition. A simple, benign and highly efficient ultrasound-mediated route was designed to produce chromene derivatives via one-pot, multicomponent reaction of aldehyde, malononitrile, and resorcinol at room temperature. The ultrasound-mediated synthetic route was studied here exhibits some remarkable advantages such as short reaction times, green reaction conditions, operational simplicity, high yields, and easy work-up and purification steps. In addition to this interestingly found that there was unnoticeable loss of reactivity when the catalyst was quantitatively recovered from the reaction medium and recycled up to five times. [ABSTRACT FROM AUTHOR]

The peculiar one-pot reaction involving Carbaldehydes, malononitrile, and indane 1,3-dione was used to explain the alternative synthesis of indeno-pyridine and indeno-pyran derivatives. The synthesis of indeno-pyridine or indeno-pyran derivatives has been examined based on an effective modification in the Michael addition of indane 1,3-dione or malononitrile on Knoevenagel product throughout the reaction process. The reaction required up to 30 min to complete utilizing CuO nanoparticles (NPs) in water at room temperature, making the approach innovative and environmentally benign. All of the produced compounds have been validated using spectroscopic data. And they were then tested for their antimicrobial activities. All tested compounds showing greater efficacy against Sertaconazol and Chloramphenicol. [ABSTRACT FROM AUTHOR]

AbstractA multicomponent technique was utilized to synthesize pyrroloimidazoles, a novel class of compounds, with exceptional efficiency. The reaction involved the combination of oxoindolinylidene malononitrile, ethyl 2-arylamino-4-dioxo-4-arylbutanoates, hydrazonoyl chlorides, ammonium acetate, and ethyl bromopyruvate in an aqueous solution at room temperature. The presence of Ag/Fe3O4@MWCNTs MNCs intensified the reaction. This study examines the antioxidant properties of pyrroloimidazoles, in addition to other investigations undertaken within the same study. The manufacture of pyrroloimidazole exhibited several advantageous characteristics, such as rapid reactions, elevated yields of the end product, and straightforward separation of the catalyst and product from the reaction mixture. [ABSTRACT FROM AUTHOR]

A green and efficient method for the preparation of spirooxindole‐linked fused pyrans has been developed utilizing a catalyst‐free visible‐light‐driven one‐pot multicomponent reaction strategy. The reaction was performed in a water and ethanol mixture, using the combination of isatin, malononitrile, and cyclic 1,3‐dicarbonyls such as 4‐hydroxy‐1‐methyl‐2(1H)‐quinolone, 4‐hydroxycoumarin, 4‐hydroxythiocoumarin, or barbituric acid derivatives. This catalyst‐free, environmentally friendly, visible‐light‐driven, and room temperature method is a valuable addition to the synthetic toolbox for constructing complex heterocyclic scaffolds under one‐pot conditions. It holds promise for future applications in medicinal chemistry and drug discovery. [ABSTRACT FROM AUTHOR]

Context: Indandione-based materials are promising candidates for organic electronics, offering high electron mobility and tunable optoelectronic properties. In this study, we explore the optoelectronic and photovoltaic properties of indandione-based donor–acceptor (D-A) materials, specifically (R1) and (R2), by introducing malononitrile group acceptors into their molecular structure. These strong electron-withdrawing acceptors are designed to enhance charge transfer and overall material performance. The designed molecules (DM1–DM4) exhibit a low optical band gap of approximately 1.77 eV, significantly lower than the reference materials (R1 and R2) at around 2.24 eV in a solvent environment. Among the designed molecules, DM4 stands out with superior photovoltaic parameters, including a narrow optical band gap (1.77 eV), higher electron affinity (3.49 eV), an extended excited state lifetime (10.0 ns) owing to its low electron and hole reorganization energies (λe ~ 0.13 eV and λh ~ 0.24 eV), and improved short-circuit current density (Jsc) of ~ 15.73 mA/cm2. Notably, DM4 achieves a power conversion efficiency (PCE) of ~ 18.5%, making it an excellent candidate for device applications. Method: A comprehensive computational investigation was carried out on indandione-based D-A materials with malononitrile group acceptors (DM1–DM4) using density functional theory (DFT) and time-dependent DFT (TD-DFT) methods, as implemented in Gaussian 16 software. We examined the electronic and optical properties of the proposed molecules through frontier molecular orbital (FMO) analysis, UV–Vis absorption spectra, density of states (DOS), exciton binding energy (Eb), and transition density matrix (TDM) analysis, utilizing GaussView 6.0 and Multiwfn 3.8 software. The photovoltaic parameters and power conversion efficiency (PCE) were evaluated using the Scharber and Alharbi models. [ABSTRACT FROM AUTHOR]

2‐(3,6‐Bis(4‐methoxyphenyl)‐2,2,5,5‐tetramethyl‐4‐oxo‐4,5‐dihydropentalen‐1(2H)‐ylidene)malononitrile (DPM‐An) and 2,2′‐(3,6‐bis(4‐methoxyphenyl)‐2,2,5,5‐tetramethyl‐2,5‐dihydropentalene‐1,4‐diylidene)dimalononitrile (DPD‐An), both bearing the 2,5‐dihydropentalene core and intramolecular electron donor–acceptor moieties, were prepared and subjected to photophysical studies. The absorption spectra of DPM‐An and DPD‐An in CH2Cl2 at room temperature contain maxima at similar wavelengths of 406 and 409 nm, respectively. These substances do not luminesce in CH2Cl2 solution at room temperature, but they do emit light when present in poly(methyl methacrylate) films. Interestingly, DPM‐An and DPD‐An in the film forms display nearly identical emission (EM) spectra with respective maxima at 592 and 594 nm. In contrast, DPD‐An has a longer EM lifetime than does DPM‐An. Therefore, the dihydropentalene derivatives, exemplified by DPM‐An and DPD‐An, may be a family of substances in which excited state decay rate can be varied without changing EM wavelengths. [ABSTRACT FROM AUTHOR]

A dicyanoisophorone based fluorescent probe (E)‐2‐(3‐(4‐hydroxystyryl)‐5,5‐dimethylcyclohex‐2‐en‐1‐ylidene)malononitrile (DCIP‐OH) was developed for the selective sensing of tyrosinase in apple extract and live cells. The probe was obtained by the condensation of 2‐(3,5,5‐trimethylcyclohex‐2‐en‐1‐ylidene)malononitrile with 4‐hydroxybenzaldehyde. Upon interaction with tyrosinase, the probe exhibited absorbance switching from 417 nm to 357 nm, accompanied by a slight increase in absorption value and an isosbestic point observed at 373 nm. Additionally, a reduction in emission intensity at 592 nm was observed. Furthermore, we successfully employed the probe for sensing of tyrosinase in apple extract and conducted inhibition studies by using kojic acid. LOD was determined to be ~0.4 nM. Moreover, the biocompatible nature of DCIP‐OH enabled its effective localization in epithelial‐like melanoma cells, B16F10, where it demonstrated successful fluorescent probing of intracellular tyrosinase. [ABSTRACT FROM AUTHOR]

A series of substituted 2-aminotetrahydroquinolinecarbonitriles have been synthesized by the three-component condensation of diaryl(hetaryl)methylidenecyclohexanones, malononitrile, and ammonium acetate. Factors responsible for the reaction selectivity and product formation pathway have been revealed. The reaction of aminoquinolinecarbonitriles with acetic anhydride under acidic conditions afforded substituted hexahydro-pyrimido[4,5-b]quinolinones. The structure of the synthesized compounds has been determined by IR and 1H and 13C NMR spectroscopy, including HSQC two-dimensional correlation technique. [ABSTRACT FROM AUTHOR]

This study synthesized 1,6‐naphthyridine as a novel class of fused heterocyclic compounds with high efficiency using a multicomponent reaction. The reaction involved benzaldehyde or its derivatives, 2 mol of malononitrile, and 4‐aminocumarin in an aqueous solution at room temperature in the presence of SiO2/Fe3O4@MWCNTs as a recyclable catalyst. This study examines the antioxidant properties of 1,6‐naphthyridine in addition to the other research undertaken in this work. The production process of 1,6‐naphthyridine demonstrated several advantageous features, including rapid reactions, high yields of the final product, and straightforward separation of the catalyst and product from the reaction mixture. [ABSTRACT FROM AUTHOR]

A highly effective oxidation cross-coupling method involving para -cresol derivatives and malononitrile derivatives has been developed utilizing undivided electrolytic conditions. This electrochemical approach offers a robust route for synthesizing diverse malononitrile derivatives featuring quaternary carbon centers and incorporating para -phenol groups. Notably, the direct electrooxidation of the C(sp3)–H bond in the para -cresol derivative plays a crucial role in this process under electrolytic conditions. Various para -cresol derivatives and malononitrile derivatives with different substituents are readily compatible with this electrochemical transformation, affording coupling compounds in up to 99% yield. [ABSTRACT FROM AUTHOR]

Polysubstituted derivatives of pyrans, chromenes, and chromeno[2,3-b]pyridines incorporating a 4,5-dichloroisothiazole or 5-arylisoxazole-3-carbaldehyde fragment in the molecule were synthesized by successive and one-step three-component reactions of 4,5-dichloroisothiazole-3-carbaldehyde and 5-arylisoxazole-3-carbaldehyde with various 1,3-diketones, malononitrile or its dimer. The structure of the target products was proven by X-ray structural analysis. Notably, it was found that the planes of the azole and chromene rings in the molecules of (1,2-azol-3-yl)chromenes are almost perpendicular. Intrinsic antitumor activity and synergistic enhancement of the activity in combination with known cytostatics used in the therapy of oncological diseases were found for some of the synthesized compounds. [ABSTRACT FROM AUTHOR]

We herein reported a sustainable synthesis of 3,3-disubstituted oxindoles via a Michael-type reaction based on the CuBr-catalysed capture of carboxylic oxonium ylides with isatylidene malononitrile. The reaction is characterized by a high atom economy and low economic constraints. The catalyst CuBr could be conveniently recyclized. The products of the reaction were found to be inhibitory against Na ion channels. We expect the reaction to shed the light on synthesis of biologically interesting molecules directed by principles of green chemistry. [ABSTRACT FROM AUTHOR]

The synthesis of 2‐amino‐1,4‐dihydropyridines was accomplished starting from β‐enaminones, aromatic aldehydes and malononitrile with DBU and without solvent. The reaction proceeds through a Knoevenegel condensation, which affords the benzylidine olefin intermediate. This can directly react with β‐enaminone, leading to the desired product. Simple reaction conditions with no solvent and good yields are the advantages of this protocol. [ABSTRACT FROM AUTHOR]

Photoactive conjugated microporous polymers (CMPs) as heterogeneous photocatalysts provide a sustainable alternative to classical metal‐based semiconductor photosensitizers. However, previously reported CMPs are typically synthesized through metal catalyzed coupling reactions, which bears product separation, but also increases the price of materials. Herein, a new type of sp2 carbon linked DCM‐CMPs are successfully designed and synthesized by organic base catalyzed Knoevenagel reaction using 2,6‐Dimethyl‐4H‐pyran‐4‐ylidene‐malononitrile and aromatic polyaldehydes as monomers. The new polymers feature inherent porosity, excellent stability, and fully π‐conjugated skeleton with broad visible‐light absorption. They effectively induce the synthesis of benzimidazole compounds under light irradiation, and exhibit wide substrate adaptability with outstanding recyclability. [ABSTRACT FROM AUTHOR]

An organocatalyzed three‐component protocol using diazoacetonitrile to access a wide range of cyanopyrazole derivatives is reported here. This strategy, which proceeds through a piperidine‐catalyzed Knoevenagel condensation/formal [3+2] cycloaddition/dehydrocyanation sequence, provides an efficient route to construct dicyanopyrazoles from aldehydes, malononitrile, and diazoacetonitrile regioselectively. Interestingly, by engaging cyanoacetate and cyanoacetamide in this protocol, we could achieve cyanopyrazole esters and carboxamides. [ABSTRACT FROM AUTHOR]

Chemical compounds, such as the CS gas employed in military operations, have a number of characteristics that impact the ecosystem by upsetting its natural balance. In this work, the toxicity limit and microorganism's reaction to the oxidative stress induced by O-chlorobenzylidenemalonitrile, a chemical found in CS gas, were assessed in relation to the green algae Chlorella pyrenoidosa. A number of parameters, including the cell growth curve, the percent inhibition in yield, the dry cell weight, the percentage viability and productivity of algal biomass flocculation activity, and the change in oxygen production, were analyzed in order to comprehend the toxicological mechanisms of O-chlorobenzylidenemalonitrile on algal culture. Using fluorescence and Fourier transform infrared spectroscopy (FTIR), the content of chlorophyll pigments was determined. The values obtained for pH during the adaptation period of the C. pyrenoidosa culture were between 6.0 and 6.8, O2 had values between 6.5 and 7.0 mg/L, and the conductivity was 165–210 µS/cm. For the 20 µg/mL O-chlorobenzylidenemalonitrile concentration, the cell viability percentage was over 97.4%, and for the 150 µg/mL O-chlorobenzylidenemalonitrile concentration was 74%. The ECb50 value for C. pyrenoidosa was determined from the slope of the calibration curve; it was estimated by extrapolation to the value of 298.24 µg/mL. With the help of this study, basic information on the toxicity of O-chlorobenzylidenemalonitrile to aquatic creatures will be available, which will serve as a foundation for evaluating the possible effects on aquatic ecosystems. The management of the decontamination of the impacted areas could take the results into consideration. [ABSTRACT FROM AUTHOR]

Recently, the construction of the trisubstituted olefin-type probe molecules has elicited the attention of many researchers. However, the synthesis of the trisubstituted olefin-type probes containing two N-heterocycles simultaneously has been rarely reported. In this study, starting from the inexpensive mucobromic acid 1 and N-heterocyclic compound 2, we first utilized a simple one-step reaction to synthesize a series of trisubstituted olefin-type compounds 3 simultaneously bearing with the structure of two N-heterocyclic rings in the absence of transition metal catalysts with a yield of 62–86%. The optimal reaction conditions were systematically explored, and the structure of the obtained compounds 3 were well characterized with 1H NMR, 13C NMR, X-ray single-crystal and HR-MS. The preliminary observation showed that, in the presence of base, mucobromic acid 1 reacts as its ring-opening structure, and the successive nucleophilic substitution reaction and Michael addition reaction can generate the target product 3. Considering that the aldehyde group in the molecular structure of the trisubstituted olefin-type compounds 3 may react with malononitrile, we carried out some relevant investigations so as to realize the visual detection of malononitrile. Interestingly, among the products, compounds 3a–3c can be prepared in portable test strips through a simple process and used to achieve the naked-eye detection of malononitrile in environmental systems as designed. [ABSTRACT FROM AUTHOR]

Pyrazolophthalazines and their derivatives are known as a substance with diverse chemical and biological activity. These compounds have various medicinal properties such as antibacterial, anti-viral, anti-coagulant and anti-cancer. In this research synthesis of Pyrazolophthalazine derivatives by reaction of aromatic aldehyde derivatives, Phthal hydrazide and malononitrile in the presence of Hercynite as nano-catalyst were studied and the products were obtained in 45-90 minutes with yield of 90-97%. The structure of Hercynite nanocatalyst was investigated using FT-IR and SEM methods and X-ray diffraction pattern. The results of the morphology of the nanocatalyst surface show that the nanoparticles are spherical and the size of the particles is between 49-80 nm. Investigating the magnetic property of the catalyst with VSM analysis shows the favorable magnetic property of Hercynite nanocatalyst for its separation with an external magnetic field. Easy operation, high efficiency, reuse of the catalyst for several times, short reaction time and easy separation of the catalyst using an external magnet are the most important advantages of the presented method. [ABSTRACT FROM AUTHOR]

Type II topoisomerases (TOP2s) play a key role in altering the DNA topology by transiently cleaving both strands of a DNA duplex. Therefore, increased TOP2 activity is associated with many cancers. Herein, we present the synthesis, structural characterization, virtual screening, and structural exploration, as well as evaluation of the antiproliferative effects of two new 4-substituted 2-(5,5-dimethyl-3-styrylcyclohex-2-enylidene)malononitrile derivatives with potential application in the drug design of isoform-specific TOP2 inhibitors. Both compounds 1 and 2 were verified by ESI-TOF-MS, NMR, and single-crystal X-ray diffraction (SCXRD) analysis. Furthermore, we applied our recently proposed SCXRD/HYdrogen DEsolvation (HYDE) technology platform in order to perform molecular modeling, virtual screening, and structural exploration with 1 and 2. For this purpose, we used the crystal structure of human TOP2β complexed to DNA and the anticancer drug etoposide. Moreover, we further evaluated the antiproliferative activity of 1 and 2 on human hepatocarcinoma HepG2 cells and compared the observed effects with those of the reference hTOP2β inhibitor etoposide. Based on the obtained results, compounds 1 and 2 showed a virtually higher binding affinity (Ki HYDE values) over etoposide towards hTOP2β but lower antiproliferative activity compared to those of etoposide. [ABSTRACT FROM AUTHOR]

The synthesis and properties of a series of 11,11,12,12‐tetracyano‐9,10‐anthraquinodimethane (TCAQ) inspired electron acceptors based on thiophene‐fused quinone and triptycene motifs is presented. This has yielded insights into structure‐property relationships for establishing and modulating simultaneous two‐electron reduction processes in TCAQ analogues. These new compounds were synthesised using a Friedel‐Crafts acylation between triptycene and thiophene‐3,4‐dicarbonyl chloride. Isomeric para‐quinones featuring a [c]‐fused thiophene on one side and a β,β‐ or α,β‐fused triptycene on the other were isolated alongside a thiophene‐3,4‐diketone which bears two triptycene fragments. Knoevenagel condensation of these products with malononitrile produced a quinoidal bis(dicyanomethylene), an oxo‐dicyanomethylene and an acyclic bis(dicyanomethylene). This series of new electron accepting molecules has been studied using X‐ray crystallography and the implications of their 3D structures on NMR and UV/vis absorbance spectroscopy and cyclic voltammetry results have been ascertained with conclusions underpinned by computational methods. [ABSTRACT FROM AUTHOR]

This study depicts the synthesis of a novel biocatalyst Cluster Fig Ash (CFA) from cluster fig. XRD, FT‐IR, EDX, TGA, BET and SEM techniques were used to characterize the synthesized CFA catalyst. The one‐pot multicomponent synthesis of pyrano[2,3‐c]pyrazoles derivatives under ambient conditions was utilised to test the catalytic activity of this synthesized CFA biocatalyst. It was found that an easy, reliable, and extremely efficient method has been proposed to synthesise pyrano[2,3‐c]pyrazoles derivatives using one‐pot, multicomponent reaction involving aldehyde, malononitrile, ethylacetoacetate, and Hydrazine monohydrate. [ABSTRACT FROM AUTHOR]

New approaches based on multicomponent condensation reactions were proposed to the synthesis of new heterocyclic derivatives of malononitrile dimer of the series of 7-oxa-1,3,6-triazabenzo[no]tetraphene, 1,2,3,4-tetrahydropyrazolo[1,5-a][1,3,5]triazine, 1,3,5,5-tetracyanocyclohex-3-ene, 3,9-diazaspiro[5.5]undeca-1,4-diene and 1Н,5Н-spiro[3,7-diazabicyclo[3.3.1]non-2-ene-9,4'-piperidine]. Structure of the products was studied using mass spectrometry, IR and NMR spectroscopy, as well as X-ray diffraction analysis. [ABSTRACT FROM AUTHOR]

The immobilization of homogeneous catalytic material over suitable heterogeneous support is amongst the recent strategies to minimize the shortcomings and unite the merits of homogeneous and heterogeneous catalysts. However, the physisorption-based immobilization does not serve the purpose because of its temperature as well as solvent dependent highly reversible nature. In the present work, a new catalytic material silica bonded bis(hydrogensulphato)benzene (SiO2-BHSB) was developed through the chemisorption of benzene-1,3-disulfonic acid as an active catalytic material over the surface of micro-sized silica. The synthesis, structure, purity, thermal stability and acid strength of the newly synthesized catalytic material were confirmed by appropriate analytical techniques such as solid-state CP-MAS 13C-NMR, CP-MAS 29Si-NMR, FT-IR, EDX, TGA, DSC and volumetric studies. An efficient and environmentally benign catalytic protocol for the synthesis of highly substituted 4H-pyran scaffolds was developed, in which a small amount of SiO2-BHSB (3 mol%) was observed sufficient to promote a tandem reaction between alkyl acetoacetate, malononitrile and structurally diverse aldehydes to offer good to excellent yields of 4H-pyran derivatives in aqueous based solvent. Structures of the synthesized 4H-pyran derivatives were confirmed by suitable characterization techniques. The catalytic material was observed to have enough catalytic potential to exhibit sustained catalytic activity even after five cycles of its reuse. Features such as presence of two -SO3H groups, strong acidic character, organo–inorganic hybrid nature, highly stable and chemically inert silica base, high heat of adsorption, large surface area and effective pore volume make SiO2-BHSB a versatile and convenient catalytic material. Herein described catalytic protocol stood better in terms of convenient recovery and reuse of catalyst, waste minimization, environment safety, aqueous based solvent, normal energy conditions and operational simplicity than majority of the cited protocols. [ABSTRACT FROM AUTHOR]

An effective environmentally friendly procedure has been proposed for the synthesis of novel bioactive 2-amino-4H-chromene derivatives by one-pot three-component condensation of aromatic aldehydes, malononitrile, and cyclohexane-1,3-dione using tetrabutylammonium hydrogen sulfate (TBAHS) as a catalyst under reflux conditions. The product structure was confirmed by IR, 1H and 13C NMR, and mass spectroscopic techniques. Simple workup procedure, excellent yields, and short reaction times are the most attractive benefits of the proposed multicomponent approach. [ABSTRACT FROM AUTHOR]

This study looked into the high yield production of new spiropyrrolooxindole derivatives. In order to create these new compounds, a multicomponent reaction involving isatin, malononitrile, alkyl 2,4-dioxo-4-(arylamino) butanoate derivatives, primary amines, and ethyl bromopyruvate was carried out in water at room temperature with catalytic amounts of Ag@KF/CP NPs acting as a high performance catalyst. The antioxidant property of new synthesized spiropyrrolooxindoles are owing to having NH group which was evaluated by two procedures. Also, the antimicrobial activity of new generated spiro isatins was evaluated by disk distribution process utilizing two kinds of Gram-negative bacteria and Gram-positive bacteria; proving bacterial growth was stopped by using of these compounds. Also, the catalytic activity of the green synthesized Ag@KF/CP NPs was evaluated in the reduction of organic pollutants such as 4-nitrophenol (4-NP) in water at mild conditions. The results indicated that the biosynthesized NCs have very high and effective catalytic activity for organic pollutants within few seconds. Applied to the preparation of spiropyrrolooxindole derivatives, this method has short reaction times, high product yields, and the ability to separate catalyst and product using simple procedures. The spiropyrrolooxindoles can be found in many molecules of biological or pharmaceutical interest. Multicomponent reactions (MCRs) are a more interesting type of reaction due to mixing three or more reactants in one-pot and generating one product and economically useful and environmentally secure than to multi-step methods. Carrying out synthesis of organic compounds in water media is very interesting because of water is cheap solvent, more available with high amounts. [ABSTRACT FROM AUTHOR]

In the present study, we have synthesized TBAVIL@nano-SiO2 as a novel heterogeneous catalytic system by using tetrabutylammonium valinate ionic liquid (TBAVIL) and silica nanoparticles. The designed catalytic system is used for the preparation of naphthopyran derivatives by reacting substituted aromatic aldehyde, β-naphthol, and malononitrile in one pot system without the addition of solvent and co-catalyst. This method affords excellent yield (85–96%) of all the products with less reaction time (7–42 min). The catalyst reusability is also checked up to five cycles and found to have excellent activity up to three cycles. [ABSTRACT FROM AUTHOR]

A new efficient approach to the synthesis of intensely colored 2‐(2‐oxo‐3H‐pyrrol‐3‐ylidene)malononitrile (OP) was developed. Using the reaction of OP with amines, a series of previously unknown colorless organic salts – dicyano(2‐oxo‐2,5‐dihydro‐1H‐pyrrol‐3‐yl)methanides were synthesized, bearing in the structure two fragments of same or diverse amines of different nature (covalent and ionic). TGA‐DTA study of the synthesized salts showed a thermal reversibility of their formation. The introduction of violet OP into paper followed by treatment with amine vapors revealed prospects of using such a system for naked‐eye detection of volatile amines. It was also shown that OP‐based rewritable paper can be created, to which a data can be applied by local heating and erased by the action of amine or temperature. [ABSTRACT FROM AUTHOR]

Three-component reaction between sodium azide, ethyl cyanoacetate or malonitrile and arylglyoxals afforded 4,5-disubstituted 1,2,3-triazole derivatives in high yields. All reactions were conducted in ethanol as an environmentally benign solvent at room temperature without using any catalyst or modifier. Stable solid products were easily isolated and purified by washing with water and diethyl ether. The structures of the compounds were proved by 1H and 13C NMR and IR spectral and elemental analysis data. [ABSTRACT FROM AUTHOR]

A method for obtaining new donor-acceptor polyene chromophores, 2-amino-6-aryl-6-chlorohexa-1,3,5-triene-1,1,3-tricarbonitriles, was developed. Investigation of their optical properties revealed absorption maxima in a chloroform solution, ranging widely from 365 to 517 nm, while the emission maxima were observed in the 612–659 nm range. Luminescence in the solid state was found to occur in the range of 605 to 760 nm. [ABSTRACT FROM AUTHOR]

Zinc ferrite (ZnFe2O4) nanoparticles were synthesized in the presence of naturally available lemon juice. The synthesized zinc ferrite nanoparticles were characterized by FT-IR, XRD, SEM, TEM, TG-DTA, EDX, and BET techniques. The ZnFe2O4 is highly efficient, cheap, and reusable nanocatalyst. The zinc ferrite nanoparticles were used for the synthesis of 1H-pyrazolo[1,2-b] phthalazine-5,10-dione derivatives by one-pot coupling reaction of phthalhydrazide, aromatic aldehyde, and malononitrile under conventional reflux condition. This green synthetic approach offers important features like use of non-toxic substances, maximum yields in short reaction time, and easy purification of product. [ABSTRACT FROM AUTHOR]

2‐(1‐Hydroxyethylidene)malononitrile (4) is commercially sold as the keto isomer and is described in the literature as either a keto (4 b) or enol (4 a) species. Using NMR techniques and single crystal X‐ray diffraction, we were able to show that 4 exists exclusively as the enol isomer (4 a) in solution as well as in the solid state, which agrees with quantum chemical calculations. By adding one or two equivalents of the Lewis acid B(C6F5)3, the mono‐ or diadducts are formed in exergonic reactions, in which the enol form is further thermodynamically stabilized. The structure and acidity of enol 4 a and its borane adducts are discussed based on experimental and theoretical results. [ABSTRACT FROM AUTHOR]

2‐(1‐Hydroxyethylidene)malononitrile (4) is commercially sold as the keto isomer and is described in the literature as either a keto (4 b) or enol (4 a) species. Using NMR techniques and single crystal X‐ray diffraction, we were able to show that 4 exists exclusively as the enol isomer (4 a) in solution as well as in the solid state, which agrees with quantum chemical calculations. By adding one or two equivalents of the Lewis acid B(C6F5)3, the mono‐ or diadducts are formed in exergonic reactions, in which the enol form is further thermodynamically stabilized. The structure and acidity of enol 4 a and its borane adducts are discussed based on experimental and theoretical results. [ABSTRACT FROM AUTHOR]

We developed an oxidative synthetic method for α‐nitroketones from α‐substituted malononitriles and nitromethane under molecular oxygen. Only base and molecular oxygen are necessary without condensation reagents; this is an environmentally benign synthesis. [ABSTRACT FROM AUTHOR]

A DBN promoted [4+2] cycloaddition of malononitrile with 2‐(3‐oxo‐3‐arylprop‐1‐en‐1‐yl)phenyl buta‐2,3‐dienoates has been developed. This protocol provides a simple strategy for the construction of 2‐amino‐4‐(2‐oxo‐2‐phenylethyl)‐4H‐chromene‐3‐carbonitriles in moderate to good yields. [ABSTRACT FROM AUTHOR]

We have developed a simple and efficient method for synthesizing 2-amino-4,8-dihydropyrano[3,2-b]pyran-3-carbonitriles using catalytic role of recyclable PEG-400 and glycerol at 100 ºC. A total of 15 kojic acid derivatives were synthesized via a one-pot three-component reaction between substituted aromatic aldehydes, malononitrile, and kojic acid with good to excellent yields ranging from 70 to 94% within 0.5–5 h using PEG-400 and 1–6 h using glycerol. The method is characterized by operational simplicity, high yields, and an easy work-up process, as well as being environmentally friendly and avoiding the use of complex catalysts and toxic solvents. Furthermore, the protocol allows for the recycling of PEG-400 and glycerol and can be reused for up to three cycles without appreciable loss in reactivity. We have performed an in-silico study of all the synthesized compounds. Based on the in-silico study, compounds 4ao, 4aa, 4ai, and 4ah showed the better binding affinity towards DNA gyrase protein and these four compounds demonstrates their potential as drug-like molecules by complying with Lipinski's rule and Jorgensen's rule, and all their pharmacokinetic parameters were within the acceptable range. [ABSTRACT FROM AUTHOR]

Substituted 2,3,4,5,6,7-hexahydro-1-benzofuran-3,3-dicarbonitriles were obtained by the three-component condensation of 2-bromodimedone, aromatic aldehydes, and malononitrile. [ABSTRACT FROM AUTHOR]

An efficient, one-pot quantitative procedure for the preparation of benzo[a]pyrano[2,3-c]phenazine derivatives from four-component condensation reaction of 2-hydroxynaphthalene-1,4-dione, benzene-1,2-diamine, aromatic aldehydes, and malononitrile in the presence of [(EtO)3Si(CH2)3N+H3][CH3COO−] as basic ionic liquid as catalyst in homogenous solution under solvent-free conditions at 90 °C is described. Simple procedure, high yields, short reaction times, and an environmentally benign method are advantages of this protocol. The [(EtO)3Si(CH2)3N+H3][CH3COO−] can be recovered and reused several times without loss of its activity. [ABSTRACT FROM AUTHOR]

N,N'-(methylenebis(1,4-phenylene))bis-(2-cyanoacetamide) was exploited as a precursor for synthesing some bis (benzylidene 5a-c, pyridines 7,8,10a,b, chromene 14, benzochromene 15) derivatives containing diphenyl-methylene spacer via the reaction with each of aromatic aldehydes, pentane-2,4-dione, acetaldehyde/malononitrile, arylidene-malononitriles, ethyl cinnamates, 2-hydroxybenzaldehyde, and 2-hydroxy-1-naphthaldehyde). Bis(chromeno[3,4-c]pyridines 16 & 18) were synthesized via Michael's addition of malononitrile or ethyl cyanoacetate to Bis(chromene) derivative. The newly prepared compound structures were established via ir, NMR spectroscopic data. [ABSTRACT FROM AUTHOR]

Cycloparaphenylenes (CPPs) are the smallest possible armchair carbon nanotubes, the properties of which strongly depend on their ring size. They can be further tuned by either peripheral functionalization or by replacing phenylene rings for other aromatic units. Here we show how four novel donor–acceptor chromophores were obtained by incorporating fluorenone or 2‐(9H‐fluoren‐9‐ylidene)malononitrile into the loops of two differently sized CPPs. Synthetically, we managed to perform late‐stage functionalization of the fluorenone‐based rings by high‐yielding Knoevenagel condensations. The structures were confirmed by X‐ray crystallographic analyses, which revealed that replacing a phenylene for a fused‐ring‐system acceptor introduces additional strain. The donor–acceptor characters of the CPPs were supported by absorption and fluorescence spectroscopic studies, electrochemical studies (displaying the CPPs as multi‐redox systems undergoing reversible or quasi‐reversible redox events), as well as by computations. The oligophenylene parts were found to comprise the electron donor units of the macrocycles and the fluorenone parts the acceptor units. [ABSTRACT FROM AUTHOR]

A potential DIPEA‐assisted approach has been unfolded for the synthesis of novel β‐carboline tethered‐4H‐pyran derivatives via one‐pot condensation of 1‐formyl‐9H‐β‐carbolines, β‐keto esters and malononitrile in ethanol at ambient temperature. A library of 28 new β‐carboline tethered 4H‐pyran derivatives has been developed. The significant features of the present strategy include high efficiency, excellent yield, inexpensive catalyst, mild reaction conditions, multicomponent character of reaction and simple purification procedure. [ABSTRACT FROM AUTHOR]

An efficient, one-pot, and catalyst-free pathway was reported for the synthesis of novel chromeno[1,6]naphthyridine derivatives via a multicomponent condensation reaction of salicylaldehyde derivatives, malononitrile dimer, and active methylene compounds. All the reactions were performed in polyethylene glycol-400 as a green solvent at 80 °C. The reactions proceeded with a high-atom economy, and new products were synthesized with good yields and a simple work-up procedure, with water as the only by-product. [ABSTRACT FROM AUTHOR]

A novel one-pot, three-component reaction of 2-aminothiophenols, aldehydes and malononitrile was studied under electrochemical conditions. The reaction was conducted using TBABF4 as an electrolyte and CuI as a catalyst in an undivided cell at room temperature. The proposed reaction mechanism showed that CuI acted as an "electron relay". [ABSTRACT FROM AUTHOR]

We have described one-pot multicomponent synthesis of 2-amino-3,5-dicyano-6-phenylthiopyridine incorporated1,2,3-triazole derivatives from triazolyl aldehydes, malononitrile and thiophenol in excellent yields. The antitubercular, antifungal and antioxidant activity for all the synthesized derivatives were evaluated. The antifungal activity results show that the compounds 12a, 12b and 12g were observed more potent than Miconazole with MIC value <25 µg/mL. Whereas, the antitubercular screening against MTB H37Rv strain did not produce any promising results. Furthermore, in silico ADME properties for all the compounds were also studied and exhibited the potential to be developed as an oral drug candidate. [ABSTRACT FROM AUTHOR]

New thiadiazole-pyrazolotriazine and thiadiazole-pyrazolopyrimidine hybrids were produced by heterocyclization reactions of aminopyrazole-thiadiazole hybrid with various active methylene compounds and/or unsaturated nitriles. The configuration and energy of the DFT predicted frontier molecular orbitals of the produced hybrids were investigated and hybrids with a low energy gap (ΔEH−L) offered better biological activity. The in vitro anticancer activity of the synthesized compounds was examined against four cancer cell lines (MCF-7, PC3, Hep-2, and HepG2) as well as normal fibroblast cells (WI38). The hybrids 6, 7, 8, and 9 revealed strong cytotoxic efficacy toward MCF-7 cell line, IC50 = 6.54–18.36 μM, in comparison to 5-Fu with IC50 = 5.39 ± 0.52 μM. The structural activity relationship (SAR) and Multiple Linear Regression (MLR) studies have been performed to establish the relationship between anticancer efficiency and chemical structure, as well as the quantum calculated parameters. Furthermore, the in silico docking studies were employed to simulate breast hormone signaling with (PDB:5NQR). [ABSTRACT FROM AUTHOR]

The main aim of the current research is directed to find a suitable approach to construct a new annulated systems namely chromeno[3′,2′:5,6]pyrido[2,3-d]pyrido[2′,3′:4,5][1,3] thiazolo[3,2-a]pyrimidines. Treatment of 3-cyano-6,8-dimethylchromone with thiobarbituric acid gave chromeno[3′,2′:5,6]pyrido[2,3-d]pyrimidine, which upon treatment with chloroacetonitrile afforded 3-aminochromenopyridothiazolopyrimidine. Vilsmeier Haack formylation of the later compound produced the desired o-aminocarboxaldehyde derivative 4. Condensation of compound 4 with some active methylene nitriles namely malononitrile, cyanoacetamide, ethyl cyanoacetate, cyanoacetamide, N-phenyl-2-cyanoacetamide, 1H-benzimidazol-2-ylacetonitrile, and malononitrile dimer produced annulated compounds 5–10 (64–76% yields). Friedländer condensation of compound 4 with some active methylene ketones namely acetylacetone, ethyl cyanoacetate, diethyl malonate, and acetoacetanilide afforded annulated systems 12–15 (65–71% yields). During in vitro examination of the prepared compounds against antimicrobial activity, they appeared high activity against yeast, fungus strains and intermediate activity against all types of bacterial strains. The poly-functional product 10 exhibited notable efficiency against all types of the used microorganisms, while compound 4 present high activity against Gram-positive, yeast and fungus strains. Using spectral and analytical data, the structures of the newly synthesized products were inferred. [ABSTRACT FROM AUTHOR]

Plant pathogenic fungi present a significant risk to crop productivity. The most cost-effective and efficient approach to mitigating plant diseases caused by these pathogenic fungi is using antifungal agrochemicals. In this study, we synthesized two sets of compounds incorporating malononitrile structures. Furthermore, we assessed the fungicidal properties of a subset of crucial intermediates and target compounds against specific agricultural fungi. Additionally, we employed predictive methods to estimate the oral LD50 values of selected target compounds in rats. The results demonstrated that the compounds E, particularly those with malononitrile and 1,2,3-triazole structures, exhibited significant inhibition (over 90%) against Rhizoctonia solani, including compound E11 with an EC50 value of 2.621 mg L−1. The toxicity prediction showed that E11 is a low-toxicity compound. Thus, E11 is a potential candidate for the further development of new R. solani selective inhibitory fungicides. [ABSTRACT FROM AUTHOR]

Due to the merits of a higher charge, an empty 4f electron layer, and a larger radius, Ln3+ ions in nanoporous LnOFs usually display a strong Lewis acidity, which endows the host frameworks with excellent catalytic performance on most of the CO2-involved reactions. Herein, a combination of [Ln2(COO)7(H2O)2] clusters (abbreviated as {Ln2}) and a multifunctional structure-oriented ligand of 4,4′,4′′-(pyridine-2,4,6-triyl)-triisophthalic acid (H6PTTA) under acidic solvothermal conditions offered a series of isomorphic nanoporous frameworks of {(Me2NH2)-[Ln2(PTTA)-(H2O)2]}n (NUC-110, Ln = Pr, Nd, Eu, Gd, Ho, Er, Tm, Yb, and Lu). Activated NUC-110 series not only own ca. 64–65% void volume composed of rare hierarchical cylindrical (17 Å) and quasi-quadrilateral (8 Å) channels and rich Lewis acid–base sites such as LnIII sites and Npyridine atoms, but also have an abnormal stability resistant to boiling water, weak acid and base solutions, and most of the organic solvents. For theoretically screening the catalytic ability of NUC-110Ln, the adsorption energy between the propylene oxide (PO) molecule and the activated host frameworks was calculated by the Dmol3 module of Material Studio software, which exhibits a binding energy between PO and NUC-110Gd, which is the smallest (−100.301 kJ/mol), suggesting that NUC-110Gd should have the most ideal catalytic performance on the cycloaddition of CO2 and epoxides. Experiments proved that the cycloaddition of CO2 and epoxides could be highly catalyzed by 0.10 mol % of NUC-110Gd catalyst under relatively mild conditions of 65 °C and 1 atm with a turnover frequency of 162 h–1. Furthermore, the Knoevenagel condensation of aldehyde and malononitrile could be accelerated by NUC-110Gd, which should be due to the fact that pyridine and defectively coordinated Gd3+ can separately activate malononitrile and aldehyde molecules. Therefore, the work not only provides a type of robust high-porosity rare-earth cluster-based MOFs but also offers a comprehensive calculation of binding energies on Ln3+ ions for the first time. [ABSTRACT FROM AUTHOR]