Green Biginelli‐type Reaction: Solvent‐free Synthesis of 5‐unsubstituted 3,4‐dihydropyrimdin‐2(1H)‐ones

The Biginelli‐type compounds, 5‐unsubstituted 3,4‐dihydropyrimdin‐2(1H)‐ones were synthesized by a one‐pot three‐component condensation of aromatic aldehydes, aromatic ketones and urea in the presence of SnCl₄ · 5H₂O under solvent‐free conditions. The advantages of this method are short reaction time (4–10 min), excellent yields (74–97%), inexpensive catalyst and solvent‐free conditions. A plausible mechanism was proposed.     

One‐Pot,Three‐Component Condensation of Aldehydes, 2‐Naphthol and 1,3‐Dicarbonyl Compounds

A practical and efficient procedure for the one‐pot multicomponent couping of aryl aldehydes, 2‐naphthol and cyclic 1,3‐dicarbonyl compounds using perchloric acid adsorbed on silica gel (HClO₄‐SiO₂) as a highly efficient, inexpensive, convenient, reusable heterogeneous catalyst under solvent‐free conditions has been developed. Various biologically important 12‐aryl‐8,9,10,12‐tetrahydrobenzo[a]xanthen‐11‐one derivatives have been efficiently synthesized in high to excellent yields. The present approach offers several advantages such as shorter reaction times, simple work‐up, excellent yields, low cost, and mild reaction conditions. Furthermore, the catalyst can be recovered simply and reused without appreciable loss of its catalytic activity.     

Synthesis of 12‐aryl‐12H‐benzo[i][1,3]‐dioxolo[4,5‐b]xanthene‐6,11‐diones using silica sulfuric acid as an efficient and versatile catalyst under solvent‐free conditions

Some novel 12‐aryl‐12H‐benzo[i][1,3]‐dioxolo[4,5‐b]xanthene‐6,11‐diones can be rapidly and efficiently synthesized in excellent yields by condensing a variety of aldehydes with 3,4‐methylenedioxyphenol and 2‐hydroxy‐1,4‐naphthoquinone in the presence of a catalytic amount of silica sulfuric acid under solvent‐free conditions. The simple experimental procedure, solvent‐free reaction conditions, utilization of an inexpensive and readily available catalyst, short period of conversion, and excellent yields are the advantages of the present method. Furthermore, the catalyst can be recycled and reused three times without significant loss of activity. The structures of the novel compounds are confirmed by IR, ¹H‐NMR, ¹³C‐NMR, MS, and elemental analysis. J. Heterocyclic Chem., 2011.     

Ionic Liquid Catalyzed One‐Pot Synthesis of 2H‐Pyridazino[1,2‐a]indazole‐1,6,9(11H)‐triones Via Three‐Component Reaction under Solvent‐Free Conditions

2H‐Pyridazino[1,2‐a]indazole‐1,6,9(11H)‐triones were synthesized through one‐pot, three‐component condesation of aldehydes, maleic hydrazide, and dimedone using a green and inexpensive Brönsted acidic ionic liquid 1‐methyl‐2‐pyrrolidinone hydrosulfate ([Hnmp]HSO₄) as catalyst under solvent‐free conditions. The method provided several advantages such as milder conditions, shorter reaction time, high yields, and environmentally benign procedure.     

Multi‐component Reactions,Solvent‐free Synthesis of Substituted Pyrano‐pyridopyrimidine under Different Conditions Using ZnO Nanoparticles

2‐Amino‐4‐(4‐substitutedphenyl)‐5‐oxo‐4H,5H‐pyrano[2,3‐d]pyrido[1,2‐a]pyrimidine‐3‐carbonitrile‐derivatives 2–12 were synthesized via multi‐component condensation reactions of different aromatic aldehydes, 3H‐pyrido[1,2‐a]pyrimidine‐2,4‐dione 1 , and malononitrile by using ZnO nanoparticles as green chemistry, environmentally friendly catalyst under solvent‐free conditions. The present work creates a variety of biologically active heterocyclic compounds in excellent yield and a short time. The structures of all synthesized compounds were elucidated with the elemental analyses, IR, ¹H NMR, and mass spectral data.     

FeCl_3: Highly Efficient Catalyst for Synthesis of α-Amino Nitriles

α‐Amino nitriles are synthesized by the three‐component coupling reaction of aldehydes, amines and trimethylsilyl cyanide using FeCl₃ as a solid acid catalyst, under solvent‐free conditions in good yields. The catalyst was recovered by simple filtration and was recycled in subsequent reactions.     

TiO2–SiO2 Catalyzed Eco‐friendly Synthesis and Antioxidant Activity of Benzopyrano[2,3‐d]pyrimidine Derivatives

A cost‐effective and eco‐friendly synthesis of benzopyrano[2,3‐d ]pyrimidine derivatives has been developed via three component one‐pot tandem approach by condensing different salicylaldehydes and secondary amines with malononitrile in the presence of TiO₂–SiO₂ catalyst at 80°C under solvent‐free conditions. Mild experimental conditions, reusability of the catalyst, and cost effectiveness are the merits of this procedure. Compounds 4g , 4h , and 4i bearing 2‐OMe group on the hydroxyphenyl group linked to the central carbon present in between the two nitrogen atoms of the pyrimidine ring were found to exhibit good antioxidant activity while other compounds have moderate antioxidant activity.     

Efficient and recyclable novel Ni‐based metal–organic framework nanostructure as catalyst for the cascade reaction of alcohol oxidation–Knoevenagel condensation

A novel Ni‐based metal–organic framework (Ni‐MOF) with a Schiff base ligand as an organic linker, Ni₃(bdda)₂(OAc)₂?6H₂O (H₂bdda = 4,4′‐[benzene‐1,4‐diylbis(methylylidenenitrilo)]dibenzoic acid), was synthesized and characterized using powder X‐ray powder diffraction, thermogravimetric analysis, Brunauer–Emmett–Teller measurements, inductively coupled plasma atomic emission spectroscopy, transmission electron microscopy, elemental analysis and Fourier transform infrared spectroscopy. The synthesized Ni‐MOF exhibited a high catalytic activity in benzyl alcohol oxidation using tert‐butyl hydroperoxide under solvent‐free conditions. Also, the efficiency of the catalyst was investigated in the cascade reaction of oxidation–Knoevanagel condensation under mild conditions. The Ni‐MOF catalyst could be recovered and reused four times without significant reduction in its catalytic activity.     

Rapid Synthesis of Novel and Known Coumarin‐3‐carboxylic Acids Using Stannous Chloride Dihydrate under Solvent‐Free Conditions

Various coumarin‐3‐carboxylic acid (=2‐oxo‐2H‐1‐benzopyran‐3‐carboxylic acid; CcaH) derivatives have been synthesized in good yields using catalytic amounts of SnCl₂?2 H₂O under solvent‐free conditions. This inexpensive, nontoxic, and readily available catalytic system (10 mol‐%) efficiently catalyzes the Knoevenagel condensation and intramolecular cyclization of various 2‐hydroxybenzaldehydes or acetophenones with Meldrum's acid. High product yields, use of inexpensive and safe catalyst, and solvent‐free conditions display both economic and environmental advantages.     

Schiff Base Structured Acid–Base Cooperative Dual Sites in an Ionic Solid Catalyst Lead to Efficient Heterogeneous Knoevenagel Condensations

An acid–base bifunctional ionic solid catalyst [PySaIm]₃PW was synthesized by the anion exchange of the ionic‐liquid (IL) precursor 1‐(2‐salicylaldimine)pyridinium bromide ([PySaIm]Br) with the Keggin‐structured sodium phosphotungstate (Na₃PW). The catalyst was characterized by FTIR, UV/Vis, XRD, SEM, Brunauer–Emmett–Teller (BET) theory, thermogravimetric analysis, ¹H NMR spectroscopy, ESI‐MS, elemental analysis, and melting points. Together with various counterparts, [PySaIm]₃PW was evaluated in Knoevenagel condensation under solvent and solvent‐free conditions. The Schiff base structure attached to the IL cation of [PySaIm]₃PW involves acidic salicyl hydroxyl and basic imine, and provides a controlled nearby position for the acid–base dual sites. The high melting and insoluble properties of [PySaIm]₃PW are relative to the large volume and high valence of PW anions, as well as the intermolecular hydrogen‐bonding networks among inorganic anions and IL cations. The ionic solid catalyst [PySaIm]₃PW leads to heterogeneous Knoevenagel condensations. In solvent‐free condensation of benzaldehyde with ethyl cyanoacetate, it exhibits a conversion of 95.8 % and a selectivity of 100 %; the conversion is even much higher than that (78.2 %) with ethanol as a solvent. The solid catalyst has a convenient recoverability with only a slight decrease in conversion following subsequent recyclings. Furthermore, the new catalyst is highly applicable to many substrates of aromatic aldehydes with activated methylene compounds. On the basis of the characterization and reaction results, a unique acid–base cooperative mechanism within a Schiff base structure is proposed and discussed, which thoroughly explains not only the highly efficient catalytic performance of [PySaIm]₃PW, but also the lower activities of various control catalysts.     

Ultrasound Promoted and Ionic Liquid Catalyzed Cyclocondensation Reaction for the Synthesis of 4(3H)-Quinazolinones

4(3H)‐Quinazolinones were synthesized in high yields by one‐pot three‐component condensation of anthranilic acid, carboxylic acid and aniline in the presence of ionic liquid such as 1‐n‐butyl‐3‐methylimidazolium tetrafluoroborate (BMImBF₄) as catalyst under solvent free and neutral conditions.     

Piperazine‐functionalized nickel ferrite nanoparticles as efficient and reusable catalysts for the solvent‐free synthesis of 2‐amino‐4H‐chromenes

Piperazine‐functionalized nickel ferrite (NiFe₂O₄) nanoparticles were synthesized as recoverable heterogeneous base catalysts using a routine method. The synthesized materials were characterized using various spectroscopic techniques such as infrared, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray, thermogravimetry analysis, and vibrating sample magnetometry. Catalytic efficiency was investigated in the synthesis of 2‐amino‐4H‐chromene derivatives via a one‐pot three component reaction of aldehyde and malononitrile with β or α‐naphthol/5‐methyle resorcinol under solvent‐free conditions with good to high yields. This method is operationally simple and has several advantages such as good to high yield, short reaction times, solvent‐free conditions, and easy synthesis. Moreover, the catalyst was recovered easily using an external magnet and reused three times without distinctive loss in catalytic activity.     

Fe3O4 Magnetic Nanoparticles (MNPs) as Reusable Catalyst for the Synthesis of Chromene Derivatives Using Multicomponent Reaction of 4‐Hydroxycumarin Basis on Cheletropic Reaction

A series of oxocyclopenta[c]chromenes were synthesized via three component reaction of 4‐hydroxycumarin, dialkyl acetylenedicarboxylate, α‐bromo ketones, and triphenylphosphine in the presence of catalytic amount of Fe₃O₄ magnetic nanoparticles (MNPs) (15 mol%) under solvent‐free conditions at 70°C. Facile, green, easy separation of product and catalyst, and high yields of products are advantages of these reactions.     

Efficient Synthesis of 1,5‐Benzodiazepine Derivatives by Ytterbium Trichloride–Catalyzed Condensation of o‐Phenylenediamine and Ketones

1,5‐Benzodiazepines are synthesized in good to excellent yields by ytterbium trichloride (YbCl₃)–catalyzed condensation of o‐phenylenediamine and ketones under mild and solvent‐free conditions. The Lewis acid–type catalyst, ytterbium trichloride, is found to be water stable and reusable.     

Green synthesis of pyrimido‐isoquinolines and pyrimido‐quinoline using ZnO nanorods as an efficient catalyst: Study of antioxidant activity

In this paper, we report the synthesis of pyrimido[2,1‐a] isoquinoline and pyrimido[1,2‐a]quinoline derivatives in high yields from the reaction of isoquinoline or quinoline, activated acetylenic compounds, and amides in the presence of ZnO nanorods (ZnO‐NRs) as catalyst under solvent‐free conditions at room temperature. ZnO‐NRs show good improvement in the yield of the product and significant reusability. Also, the antioxidant activities of the some of the newly synthesized compounds were carried out by 1,1‐diphenyl‐2‐picrylhydrazyl (PDDH) radical trapping and ferric ion reducing potential tests and compared with those of the synthetic antioxidants 2‐tert‐butylhydroquinone (TBHQ) and butylated hydroxytoluene (BHT). These compounds do not show good DPPH radical scavenging but display good ferric ion reducing power.     

Hydrothermal preparation and characterization of ZnFe2O4 magnetic nanoparticles as an efficient heterogeneous catalyst for the synthesis of multi‐substituted imidazoles and study of their anti‐inflammatory activity

Nanoparticles are key focus of research for a wide range of novel applications. As such, ZnFe₂O₄ magnetic nanoparticles were synthesized hydrothermally and characterized via scanning and transmission electron microscopies, powder X‐ray diffraction, energy‐dispersive X‐ray and infrared spectroscopies, thermogravimetric analysis and magnetic measurements. They were used as a robust catalyst for the synthesis of a series of biologically active multi‐substituted imidazoles using a multicomponent reaction by the reaction of benzil with various aromatic aldehydes, ammonium acetate and aliphatic amines (N,N‐dimethyl‐1,3‐propanediamine and 1‐amino‐2‐propanol) under solvent‐free conditions. The key advantages of this method are shorter reaction times, very high yield and ease of operation. The thermally and chemically stable, benign and economical catalyst was easily recovered using an external magnet and reused in at least five successive runs without an appreciable loss of activity. All of these novel synthesized compounds were characterized from spectral data and their purities were checked using thin‐layer chromatography, giving one spot. Furthermore, the prepared compounds were tested for their anti‐inflammatory activity.     

Ferrocene‐tagged ionic liquid stabilized on silica‐coated magnetic nanoparticles: Efficient catalyst for the synthesis of 2‐amino‐3‐cyano‐4H‐pyran derivatives under solvent‐free conditions

An advanced novel magnetic ionic liquid based on imidazolium tagged with ferrocene, a supported ionic liquid, is introduced as a recyclable heterogeneous catalyst. Catalytic activity of the novel nanocatalyst was investigated in one‐pot three‐component reactions of various aldehydes, malononitrile and 2‐naphthol for the facile synthesis of 2‐amino‐3‐cyano‐4H‐pyran derivatives under solvent‐free conditions without additional co‐catalyst or additive in air. For this purpose, we firstly synthesized and investigated 1‐(4‐ferrocenylbutyl)‐3‐methylimidazolium acetate, [FcBuMeIm][OAc], as a novel basic ferrocene‐tagged ionic liquid. This ferrocene‐tagged ionic liquid was then linked to silica‐coated nano‐Fe₃O₄ to afford a novel heterogeneous magnetic nanocatalyst, namely [Fe₃O₄@SiO₂@Im‐Fc][OAc]. The synthesized novel catalyst was characterized using ¹H NMR, ¹³C NMR, Fourier transform infrared and energy‐dispersive X‐ray spectroscopies, X‐ray diffraction, and transmission and field emission scanning electron microscopies. Combination of some unique characteristics of ferrocene and the supported ionic liquid developed the catalytic activity in a simple, efficient, green and eco‐friendly protocol. The catalyst could be reused several times without loss of activity.     

An Efficient Synthesis of 14‐Aryl or Alkyl‐14H‐Dibenzo[a. j]Xanthenes Using Reusable HBF4‐SiO2 Catalyst Under Thermal and Solvent‐Free Conditions

A simple and convenient procedure for the synthesis of 14‐aryl or alkyl‐14H‐dibenzo[a. j]xanthene derivatives is described through a one‐pot condensation of β‐naphthol with various aryl or alkyl aldehydes in the presence of HBF₄‐SiO₂ as the catalyst under thermal and solvent‐free conditions.     

Brønsted Acidic Ionic Liquid: An Efficient and Reusable Catalyst for the Synthesis of 3,4‐Dihydropyrimidin‐2(1H)‐ones

A novel ionic liquid, 3‐carboxymethyl‐1‐methylimidazolium bisulfate (CMImHSO₄), was synthesized and used as a recyclable catalyst for the Biginelli reaction under solvent‐free conditions. High yields of various substituted 3,4‐dihydropyrimidin‐2(1H)‐ones (or thiones) were obtained. The ionic liquid can be recovered and recycled easily without loss of activity.     

A capable cobalt nano‐catalyst for the N‐formylation of various amines and its biological activity studies

The Fe₃O₄ magnetic nanoparticles (Fe₃O₄ MNPs) were modified with 1,10‐phenanthroline‐5,6‐diol and the relevant Co complex (Fe₃O₄@Phendiol@Co) synthesized as a nano‐magnetic heterogeneous catalyst to be used for the N ‐formylation of various amines at room temperature under solvent‐free conditions. Also, in order to find the better concept of the catalyst role, the N ‐formylation reaction was carried out by the use of ultrasound irradiation in the absence of the Co nano‐catalyst and the results were compared. The catalyst characterized by different methods such as the elemental analysis (CHN), ICP, FT‐IR, XRD, EDX, SEM, TEM, TG‐DTA, VSM and XPS. In addition, the antioxidant and the antibacterial activities of the Fe₃O₄@Phendiol@Co nano‐catalyst and its Phendiol ligand were in vitro screened by 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) free radical scavenging and disc diffusion methods. Results showed that they possess strong antioxidant activity (IC₅₀; 0.182 ± 0.006 mg/ml) and good antibacterial potential in comparison to standards.