TiO2 as a Reusable Catalyst for the One‐Pot Synthesis of 3,4‐Dihydropyrimidin‐2(1H)‐ones under Solvent‐Free Conditions

An efficient solvent‐free method for the synthesis of various 3,4‐dihydropyrimidin‐2(1H)‐ones using TiO₂ as a recyclable heterogeneous catalyst is described. Compared to known methods, satisfactory results are obtained with excellent yields, short reaction times, and simplicity in the experimental procedure.     

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,Green and Efficient Synthesis of 3,4‐Dihydropyrimidin‐2(1H)‐ones or Thiones Catalyzed by Citric Acid

One‐pot three‐component condensation of ethyl acetoacetate, aldehyde and urea or thiourea in refluxing ethanol in the presence of catalytic amounts of citric acid afforded the corresponding 3,4‐dihydropyrimidin‐2(1H)‐ones/thiones in high yields. The catalyst is reusable and can be applied several times without any decrease in product yield.     

溴化镁催化的1,2,3,4-四氢吡啶酮无溶剂合成研究

An efficient and environmentally friendly procedure for the one-pot synthesis of tetrahydropyrimidinones from aldehydes, β-diketones and urea/thiourea by using magnesium bromide as an inexpensive and easily available catalyst under solvent-free conditions was described. Compared with the classical Biginelli reaction conditions, this new method has the advantage of good to excellent yields (74%-94%) and short reaction time (45-90 min). The structure of the Biginelli reaction product from β-diketone, salicylaldehyde and urea has been proposed to possess an oxygen-bridge by cyclization (intramolecular Michael-addition).     

Iodine Catalyzed One‐pot Synthesis of 3,4‐Dihydroquinazolin‐4‐ones from Anthranilic Acids,Ortho Esters and Amines under Solvent‐free Conditions

A simple and efficient procedure has been developed for the one‐pot synthesis of 3,4‐dihydroquinazolin‐4‐ones from anthranilic acids, ortho esters and amines using a catalytic amount of iodine under solvent‐free conditions to afford the corresponding products in excellent yields. The direct use of commercially available catalyst, mild and solvent‐free reaction conditions, short reaction time, easy workup and excellent yields are the advantages of the present protocol.     

Molecular Iodine Catalyzed One‐pot Aza‐Diels‐Alder Reaction under Solvent‐free Conditions

Catalyzed by molecular iodine at room temperature, under solvent‐free conditions, a two component aza‐Diels‐Alder cyclization of N‐vinyl‐2‐pyrrolidinone with N‐arylimine gave tetrahydroquinoline derivatives in good yields and high stereo‐selectivity. And three components aza‐Diels‐Alder reaction of N‐vinyl‐2‐pyrrolidinone, anilines and indole‐3‐carbaldehydes under the same condition afford only cis‐product in good yields.     

A Simple and Efficient One‐pot Synthesis of 1,4‐dihydropyridines Using Nano‐WO3‐ supported Sulfonic Acid as an Heterogeneous Catalyst under Solvent‐free Conditions

Nano‐tungsten trioxide‐supported sulfonic acid (n‐WSA) was found to be an effective heterogeneous cat‐ alyst for the one‐pot reaction of aromatic aldehydes, β‐dicarbonyl compounds and ammonium acetate to afford 1,4‐dihydropyridine derivatives in good to excellent yields. The other main advantages of the pres‐ ent method are short reaction times, simple workup, ease in purification and environmentally benign methodology. The reaction conditions were optimized employing Response Surface Method technique (Central Composite Design (CCD)) which is economically considerable because of the minimum number of experiments required to evaluate the effects of multiple parameters on the response.     

One‐pot Synthesis of Octahydroqinazolinones Derivatives Catalyzed by [C4(mim)2](FeCl4)2 under Solvent Free Conditions

In this investigation, a practical green chemistry procedure for synthesis of octahydroqinazolinones and thiones derivatives via condensation of aldehyde, 1,3‐cyclohexanedione/dimedone and urea or thiourea catalyzed by magnetic room temperature dicationic liquid under solvent free conditions is described. The catalyst was studied by UV spectroscopy, vibrating sample magnetometer, and thermogravimetric analysis. This methodology is of interest due to several advantages such as environmental benign, easy experimental procedure, good yield and reusable catalyst.     

Microwave‐Mediated One‐Step Synthesis of Bis(Heteroaryl‐2‐yl)Methanes from o‐Diaminoaromatics and Malonamide under Solvent‐Free Conditions

Microwave‐mediated one‐step condensations of malonamide with o‐diaminoaromatics under solvent‐free conditions generated bis(heteroaryl‐2‐yl)methanes in good yields, without use of any catalyst. Seven examples are presented, and all the reported compounds were fully characterized, among which one compound was also determined by single‐crystal crystallographic analysis.     

Ca(NO3)2•4H2O-catalysed Biginelli Reaction: One-pot Synthesis of 1,2,3,4-Tetrahydropyrimidin-2-ones/pyrimidine-2-thiones under Solvent-free Conditions

The synthesis of 1,2,3,4-dihydropyrimidinone/thione derivatives was achieved in good to excellent yields using calcium(II) nitrate as catalyst to promote the Biginelli three-component condensation reaction from a diversity of aromatic aldehydes, β-keto compounds and urea or thiourea. The reaction was carried out under solvent-free conditions.     

Ferric Hydrogensulfate Catalysed Schmidt Reaction of Ketones to Amides under Solvent‐Free Conditions

A new, efficient and convenient method has been developed for the one‐pot synthesis of amides from ketones and sodium azide in the presence of ferric hydrogensulfate in solvent‐free media. Advantages of this method are chemoselectivity, with high yields in a simple operation, and short reaction time under solvent‐free conditions.     

One‐pot Green Procedure for Synthesis of Tetrahydrobenzo[a]xanthene‐11‐one Catalyzed by Brønsted Ionic Liquids under Solvent‐free Conditions

An efficient one‐pot condensation of β‐naphthol, aldehydes and cyclic 1,3‐dicarbonyl compound has been achieved with ionic liquids as catalyst, thus a variety of 8,9,10,12‐tetrahydrobenzo[a]xanthen‐11‐one derivatives were prepared in good yields. The present approach offers several advantages such as shorter reaction times, good yields and mild reaction conditions.     

Fe3O4@SiO2‐imid‐PMAn Magnetic Porous Nanosphere as Reusable Catalyst for Synthesis of Polysubstituted Quinolines under Solvent‐free Conditions

In this research, a facile one‐pot synthesis of poly‐substituted quinoline derivatives has been demonstrated by using 2‐aminobenzophenones and ethylacetoacetate or ketones in the presence of Fe₃O₄@SiO₂‐imid‐PMAⁿ and Fe₃O₄@SiO₂‐imid‐PMA^b nanoparticles as green and reusable catalysts under solvent‐free conditions. The reaction proceeds efficiently in excellent yields and in a state of excellent purity. The nanocatalysts can be recycled and reused for at least four times without noticeably decreasing in catalytic activity.     

A Facile Synthesis of 2,2,4‐Trisubstituted‐1,2‐Dihydroquinolines Catalyzed by Zinc Triflate under Solvent‐Free Conditions

An efficient process has been developed for the synthesis of 2,2,4‐trisubstituted‐1,2‐dihydroquinolines in good yields through a simple one‐pot condensation between anilines and ketones in the presence of zinc triflate as a catalyst at room temperature under solvent‐free conditions.     

A Cheap and Efficient Methodology for the Solvent‐Free,One‐pot and Multi‐component Synthesis of 3,4‐Dihydropyrimidin‐2(1H)‐ones Catalyzed by Mesoporous NH4H2PO4/MCM‐48 and Comparison of Its Catalytic Efficacy with NH4H2PO4/MCM‐41

The catalytic efficiency of ammonium dihydrogenphosphate was evaluated in the two heterogeneous forms of NH₄H₂PO₄/MCM‐48 and NH₄H₂PO₄/MCM‐41, as mesoporous catalysts, in the solvent free synthesis of 3,4‐dihydropyrimidin‐2(1H)‐ones through one‐pot three‐component condensation of ethyl acetoacetate, an aryl aldehyde and urea. Different reaction parameters including catalytic efficacy, solvent effect, and urea concentration are considered.     

Iodine‐Catalyzed Friedlander Quinoline Synthesis under Solvent‐Free Conditions

Polyfunctional quinolines were synthesized using Friedlander method catalyzed by molecular iodine in high yields at 60 °C under solvent‐free conditions.     

New Substituted 1‐Aryl‐4,4,6‐Trimethyl‐3,4‐Dihydropyrimidine‐2‐(1H)Thiones; A Metal‐Free and Solvent‐Free Synthesis,Characterization, and Lymphoid Tyrosine Phosphatase Inhibition Studies

A series of fourteen 3,4‐dihydropyrimidine‐2‐thiones ( 3a–n ) were synthesized by a green protocol, and their structures were characterized by spectroanalytical data. The compounds were obtained in high yields by efficient annulation of mesityl oxide (4‐methylpent‐3‐en‐2‐one) with anilines in the presence of potassium thiocyanate. The reaction is essentially metal‐catalyst‐ and solvent‐free, as mesityl oxide itself is the solvent as well as the reactant. The compounds were tested for their ability to inhibit the lymphoid tyrosine phosphatase PTPN22, and 5 of the 14 compounds exhibited IC₅₀ values in the mid‐micromolar range, with the most potent hit being the compound 3d , having a methoxy substituent at the 2‐position of the phenyl ring with an IC₅₀ = 18 ± 1 μM, and second most potent compound ( 3c ) with an IC₅₀ value of 45 ± 3 μM, having methyl substituents at both 2‐ and 4‐position of the phenyl ring.     

N-Bromosuccinimide Catalyzed One-pot and Rapid Synthesis of Acetamidobenzyl Naphthols under Mild and Solvent-free Conditions

An efficient, facile and expeditious direct protocol for the preparation of acetamidobenzyl naphthols employing a multi-component and one-pot condensation reaction of 2-naphthol, benzaldehydes, and acetamide in the presence of N-bromosuccinimide (NBS) under thermal and microwave irradiation conditions has been described. The present protocol with NBS catalyst is convincingly superior to the recently reported catalytic methods.     

Unexpected One‐pot Synthesis of Novel 2‐Aminopyrimidine‐4‐ones under Microwave Irradiation

One‐pot, three‐component condensation of guanidine, ethylbenzoylacetate and various aromatic aldehydes in the presence of NaHCO₃ have been investigated by microwave irradiation. The aromatic aldehydes bearing electron‐withdrawing groups undergo condensation with guanidine and ethylbenzoyl‐acetate to afford ethyl‐2‐amino‐4‐aryl‐1,4‐dihydro‐6‐phenylpyrimidine‐5‐carboxylate derivatives via Biginelli reaction. However, reaction of the aromatic aldehydes having electron‐releasing groups with guanidine and ethylbenzoylacetate did not give the corresponding dihydropyrimidines. Instead, novel 2‐amino‐5‐benzoyl‐5,6‐dihydro‐6‐arylpyrimidine‐4(3H)‐ones were obtained via an unexpected mechanism.     

Solvent‐free Synthesis,Characterization and Solvent‐Vapor Interaction of Zinc(II) and Copper(II) Coordination Polymers containing Nitrogen‐donor Ligands

Coordination polymers of [Zn(INA)₂] ( 1 ) (INA = isonicotinate), [Cu₂(mal)₂(H₂O)₂(bipy)] ( 2 ) (mal = malonate, bipy = 4,4‐bipyridine), and [Zn₂(OAC)₄(bipy)₂] ( 3 ) (OAC = acetate) were prepared using mechanochemical grinding and heating methods. The materials were characterized with elemental analysis, FT‐IR spectroscopy, TGA, SEM, EI‐MS, BET, and PXRD. Comparison of PXRD patterns of the materials with patterns simulated from single‐crystal X‐ray diffraction data allowed identification of the products. Compared to conventional synthetic techniques such as solvothermal/hydrothermal solvent‐based methods, solvent‐free method was found to be simple, highly efficient, and environmentally friendly especially for the preparation of these coordination polymers on a large scale. Solvent‐vapor interaction properties of 1 , 2 , and 3 were investigated by exposure of the compounds to water and methanol at room temperature.