Dual Brønsted acidic-basic function immobilized on the 3D mesoporous polycalix [4]resorcinarene: As a highly recyclable catalyst for the synthesis of spiro acenaphthylene/indene heterocycles.

In this study, a novel dual Brønsted acidic-basic nano-scale porous organic polymer catalyst, PC4RA@SiPr-Pip-BuSO3H, was synthesized through various steps: preparation of a 3D network of polycalix, modification with (3-chloropropyl)-trimethoxysilane, then functionalization of polymer with piperazine and n-butyl sulfonic acid under the provided conditions. The catalyst characterization was performed by FT-IR, TGA, EDS, elemental mapping, PXRD, TEM, and FE-SEM analyses, confirming high chemical stability, activity, recoverability, and excellent covalent anchoring of functional groups. So, the designed catalyst was utilized for preparing spiro-acenaphthylene and amino-spiroindene heterocycles, providing good performance with a high yield of the corresponding products. Accordingly, this catalyst can be used in different organic transformations. Necessary experiments were conducted for the recyclability test of the polymeric catalyst, and the results showed the PC4RA@SiPr-Pip-BuSO3H catalyst can be reused 10 times without any decrease in its activity or quality with excellent stability. The structure of resultant spiro heterocycles was confirmed using 1H NMR, 13C NMR, and FT-IR.

Tungstic acid-functionalized polycalix[4]resorcinarene as a cavity-containing hyper-branched supramolecular and recoverable acidic catalyst in 4H-pyran synthesis.

In this study, tungstic acid immobilized on polycalix[4]resorcinarene, PC4RA@SiPr-OWO3H, as a mesoporous acidic solid catalyst was synthesized and investigated for its catalytic activity. Polycalix[4]resorcinarene was prepared via a reaction between formaldehyde and calix[4]resorcinarene, and then the resulting polycalix[4]resorcinarene was modified using (3-chloropropyl)trimethoxysilane (CPTMS) to obtain polycalix[4]resorcinarene@(CH2)3Cl that was finally functionalized with tungstic acid. The designed acidic catalyst was characterized by various methods including FT-IR spectroscopy, energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), elemental mapping analysis and transmission electron microscopy (TEM). The catalyst efficiency was evaluated via the preparation of 4H-pyran derivatives using dimethyl/diethyl acetylenedicarboxylate, malononitrile, and beta-carbonyl compounds, confirmed by FT-IR spectroscopy and 1H and 13C NMR spectroscopy. The synthetic catalyst was introduced as a suitable catalyst with high recycling power in 4H-pyran synthesis.

Synthesis and characterization of thiophene-derived palladium(ii) complex immobilized on FSM-16 and its application in the novel synthesis of 7-(aryl)-7,12-dihydro-6H-indeno[1,2,4]triazolo[1,5-a]pyrimidine-6-one derivatives.

The present study aims at synthesizing a palladium complex with a thiophene-carboimine ligand, supported on FSM-16 as a mesoporous silica support. Firstly, the prepared FSM-16 was modified using 3-aminopropyl group. The imine bond was subsequently formed by condensation of FSM-16-propyl amine with thiophene-2-carbaldehyde. Finally, the imine/thiophene-FSM-16 reacted with PdCl2 to form PdCl2-imine/thiophene-FSM-16. The structural and physicochemical properties of the prepared nanocomposite were characterized using FT-IR, TEM, XRD, FE-SEM, EDS, BET, and TGA analyses. PdCl2-imine/thiophene-FSM-16 exhibited efficient catalytic activity in the synthesis of indeno-1,2,4-triazolo[1,5-a]pyrimidine derivatives via a new three-component reaction between indan-1,3-dione, aromatic aldehydes and 3-amino-1H-1,2,4-triazole in water as the green solvent. Significantly, the heterogeneous catalyst can be easily separated from the reaction mixture and reused in another reaction.

Synthesis of novel pyrano[2,3-f]chromene-dione derivatives using phosphoric acid-functionalized silica-coated Fe3O4 nanoparticles as a new reusable solid acid nanocatalyst.

In this research, the synthesis of novel indeno[1,2-b]pyrano[2,3-f]chromene-2,12(13H)-dione derivatives in the presence of a newly introduced magnetically recoverable nanosolid acid catalyst is reported. At the first, phosphoric acid-functionalized silica-coated Fe3O4 nanoparticles (Fe3O4@SiO2-(CH2)3OPO3H2) were prepared and well characterized using infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), vibrating sample magnetometer (VSM), and energy-dispersive X-ray spectroscopy (EDS) techniques. Then, the catalytic activity of the prepared Fe3O4@ SiO2-(CH2)3OPO3H2 nanocatalyst was investigated for the synthesis of novel indeno[1,2-b]pyrano[2,3-f]chromene-2,12(13H)-dione derivatives via a one-pot and three-component condensation between 5,7-dihydroxy-4-methylcoumarin, indane-1, 3-dione, and various aromatic aldehydes under solvent-free condition. All the products are unknown, and their characterization was performed with the spectral data information obtained from their FT-IR, 1H and 13CNMR, elemental analysis, and their melting points. The reusability study of the introduced nanosolid acid catalyst showed that the catalytic stability is almost completely remained up to five consecutive runs.

Glucose-Decorated Silica-Molybdate Complex: A Novel Catalyst for Facile Synthesis of Pyrano[2,3-d]-Pyrimidine Derivatives.

This article describes the preparation and identification of SiO2@Glu/Si(OEt)2(CH2)3N=Mo[Mo5O18] as a new bifunctional acid-base catalyst (both acidic and basic Lewis sites). Aminopropyltriethoxysilane was first reacted with hexamolybdate anions and then treated with glucose to prepare Glu/Si(OEt)2(CH2)3N=Mo[Mo5O18]. Nano-silica was then modified by the prepared glucose/molybdate complex to obtain SiO2@Glu/Si(OEt)2(CH2)3N=Mo[Mo5O18]. The developed catalyst was characterized by FT-IR, EDX, XRD, FE-SEM and TGA analyzes. Its catalytic efficiency was investigated for the preparation of pyrano[2,3-d]pyrimidine derivatives by the reaction between various aldehydes, malononitrile and barbituric acid. The desired products were prepared in the presence of 0.004 g of the prepared catalyst in high to excellent yields.

Efficient and Facile Synthesis of Chromenopyrano[2,3-b] pyridine Derivatives Catalyzed by Sodium Carbonate.

In this research, a number of new and known chromenopyrano[2,3-b]pyridine derivatives have been prepared. Initially, according to the reported procedure, pyrano[2,3-c]chromene derivatives were synthesized by the reaction between 4-hydroxycoumarin, aromatic aldehydes and malononitrile using silica sodium carbonate (SSC) as the catalyst. Next, the prepared pyrano[2,3-c]chromenes were reacted by dimethyl acetylenedicarboxylate (DMAD) or cyclohexanone in the presence of sodium carbonate to produce chromenopyrano[2,3-b]pyridine derivatives. The presented protocol avoids the use of expensive catalysts and gives useful potentially bioactive heterocycles in excellent to high yields.

Molybdic Acid-Functionalized Nano-Fe3O4@TiO2 as a Novel and Magnetically Separable Catalyst for the Synthesis of Coumarin-Containing Sulfonamide Derivatives.

Supported molybdic acid on nano-Fe3O4@TiO2 (Fe3O4@TiO2@(CH2)3OMoO3H) has been successfully prepared, char-acterized and applied as a catalyst for the synthesis of sulfonamide containing coumarin moieties. The prepared Fe3O4nanoparticles by coprecipitation of Fe2+ and Fe3+ ions were treated with tetraethyl orthotitanate to obtain Fe3O4@TiO2. By anchoring 3-chloropropyltriethoxysilan on Fe3O4@TiO2 followed by reacting with molybdic acid, the desired catalyst was produced. The synthesized catalyst was characterized using XRD, SEM, EDS, FT-IR and VSM analysis. Fe3O4@TiO2@(CH2)3OMoO3H was used as a catalyst for the synthesis of sulfonamide containing coumarin moieties via a three-com-ponent reaction of aryl aldehydes, para-toluenesulfonamide and 4-hydroxycoumarin or 5,7-dihydroxy-4-methylcou-marin. The catalyst recovery test showed the catalyst is highly reusable without losing its activity.

A novel protocol for catalyst-free synthesis of fused six-member rings to triazole and pyrazole.

Herein, an effectual, quick and novel method is described for the synthesis of new triazolo[1,5-a]pyrimidine, triazolo[5,1-b][1,3] thiazine and pyrazolo[1,5-a]pyrimidine derivatives. This series of fused six-member rings to triazole and pyrazole was prepared via the catalyst-free reaction of dialkyl acetylenedicarboxylates and 3-substituted 1H-1,2,4-triazole or 3-amino-1H-pyrazole-4-carbonitrile. The structures of the prepared products were deduced from their Fourier-transform infrared, elemental analysis and proton and carbon-13 nuclear magnetic resonance spectral data. A novel and green method is described for the synthesis of new triazolo[1,5-a]pyrimidine, triazolo[5,1-b][1,3] thiazine and pyrazolo[1,5-a]pyrimidine derivatives.

A Green One-Pot Synthesis of 4-Hydroxychromenylarylmethyl- 6-Hydroxypyrimidine-2,4-Diones Using Titanium Dioxide Nanowires as an Effective and Recyclable Catalyst.

AIM AND OBJECTIVE: Since a wide range of biological and pharmaceutical activities of barbituric acid, 4-hydroxycoumarin and their derivatives have been disclosed until now, in the domain of our interest to find newly catalytic routes for highly efficient synthesis of potentially interesting biologically active organic compounds, and extension of their areas, herein we introduce a three component combinatorial reaction based on (N,N-dimethyl)barbituric acid and 4- hydroxycoumarin scaffolds. MATERIAL AND METHOD: All starting materials were purchased from Merck chemical company and were applied without further purifications. Catalytic reaction between barbituric acid (or N,N-dimethyl barbituric acid), 4-hydroxycoumarin, and a wide range of aryl aldehydes by employing titanium dioxide nanowires (TiO2 NWs) is successfully performed under solvent-free conditions at 100 °C, and led efficiently to obtain target products. RESULTS: From loading above mentioned three component reaction, starting materials in the presence of catalytic amounts of TiO2 NWs as a key factor were condensed together via three C-C bond formation to obtain 12 newly prepared compounds. This procedure profits some advantages such as an efficiency, environmental safety and high recyclability of nano-catalyst. CONCLUSION: In this work, by the use of a green adapted method in a condensation three component reaction catalyzed by TiO2 NWs as an efficient nano-catalyst, some newly prepared products were prepared in a one pot, and the scope of potentially interesting biologically active organic compounds which can be duly considered by biologists and pharmacologists was developed.

Silica tungstic acid as an efficient and reusable catalyst for the one-pot synthesis of 2-amino-4H-chromene derivatives.

Silica tungstic acid (STA) has been found to be an efficient and reusable solid acid catalyst for the synthesis of 2-amino-4H-chromenes via the three-component reaction of aromatic aldehydes, malononitrile, and ß-naphthol. STA as a novel solid acid was characterized by X-ray fluorescence, X-ray diffraction, and Fourier transform infrared spectroscopy.

A Rapid Synthesis of Some 1,4-aryldiazines by the Use of Lithium Chloride as an Effective Catalyst.

The synthesis of some 1,4-aryldiazines (novel and known dibenzo[a,c]phenazines and quinoxalines) based on the condensation of 1,2-aryldiamines with aromatic 1,2-dicarbonyl compounds in the presence of lithium chloride as a heterogeneous catalyst is presented as convenient and efficient strategy. This method has advantages such as excellent yields, short reaction times, and simple work-up procedure.

Fast and highly efficient solid state oxidation of thiols.

A fast and efficient solid state method for the chemoselective room temperature oxidative coupling of thiols to afford their corresponding disulfides using inexpensive and readily available moist sodium periodate as the reagent is described. The reaction was applicable to a variety of thiols giving high yields after short reaction times. Comparison of yield/time ratios of this method with some of those reported in the literature shows the superiority of this reagent over others under these conditions.

Photodegradation kinetics of some thiols and thiones in aqueous suspension of zinc oxide.

Photodegradation of several thiols and thiones including 2-pyrimidinethiol, thiazolidine-2-thione, imidazolidine-2-thione, 1,2,4- triazole 3-thiol and 2,5-dimercapto- 1,3,4-thiadiazole have been studied in aerated aqueous solution using zinc oxide under irradiation with 400W high pressure mercury lamp. Rate constants span the range from 2.44 x 10(-2) min x (-1) to 1.76 x 10(-1) min x (-1). The slower degradation rate of 2-imidazoline 2-thione could be related to oxidation potential of the corresponding ring. The Langmuir-Hinshelwood (L-H) rate constant k(r) and adsorption constant, (KA) for all five thiols and thiones are reported.

Tungstate sulfuric acid (TSA)/KMnO4 as a novel heterogeneous system for rapid deoximation.

Neat chlorosulfonic acid reacts with anhydrous sodium tungstate to give tungstate sulfuric acid (TSA), a new dibasic inorganic solid acid in which two sulfuric acid molecules connect to a tungstate moiety via a covalent bond. A variety of oximes were oxidized to their parent carbonyl compounds under mild conditions with excellent yields in short times by a heterogeneous wet TSA/KMnO4 in dichloromethane system.

Urea- hydrogen peroxide (UHP) oxidation of thiols to the corresponding disulfides promoted by maleic anhydride as mediator.

Urea-hydrogen peroxide (UHP) was used in the presence of maleic anhydride as mediator in a simple and convenient method for the oxidation in high yield of some thiols to the corresponding disulfides. Peroxymaleic acid formed in situ from the reaction of UHP with maleic anhydride has a key role in this oxidation. Performance of the reaction in various solvents showed that methanol was the solvent of choice at 0 oC. The products were isolated by simple filtration on silica gel.