无溶剂微波照射下2－取代苯并咪唑的合成

用PPA作催化剂，在无溶剂微波照射下合成了10种2－取代苯并咪唑，为该类化 合物的合成提供了一种新方法。与常规方法相比，反应时间大大缩短，产率与传统 合成方法相当。     

Nanocrystalline sulfated zirconia as an efficient solid acid catalyst for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones

The condensation reaction of 2-aminobenzamide and aldehydes or ketones was investigated in the presence of nanocrystalline sulfated zirconia (SO₄ ^2?/ZrO₂) as solid acid catalyst. SO₄ ^2?/ZrO₂ nanoparticles with different calcination temperatures were prepared and characterized by XRD, FT-IR and SEM techniques. The results confirm good stabilization of tetragonal phase of zirconia in the presence of sulfate. The reusability experiments show partial deactivation of the catalyst due to leaching of the sulfate and coke deposition on the catalyst.     

Nano sulfated titania as solid acid catalyst in direct synthesis of fatty acid amides

Nanosized sulfated titania was prepared by a sol-gel hydrothermal process. X-ray diffraction (XRD), transmission electron, and scanning electron micrographs (TEM and SEM), FT-IR specific surface area, and BET N(2) adsorption were employed to characterize the properties of the synthesized sulfated TiO(2). The results indicate that both anatase and rutile TiO(2) are obtainable. This prepared sulfated titania showed high catalytic activity in direct amidation of fatty acids as well as benzoic acids with various amines under solvent-free conditions.     

Benefits of mesopores in sulfated zirconia catalyst

Activities of two catalysts obtained from hydroxide and alkoxide precursors were correlated to their different structural and textural properties. Activity is mainly determined by the presence of active tetragonal phase, which is more stable at high temperatures in the catalyst of alkoxide origin than in one from hydroxide. An appropriate structure must be accompanied with beneficial pore structure, as is the case of mesopores of the catalyst from alkoxide. In the case of very small pores of the catalyst from hydroxide precursor, activity is negligible due to pores plugged by coke.     

Liquid-phase synthesis of 2-substituted benzimidazoles, benzoxazoles and benzothiazoles

A novel acid fluoride for use in the liquid-phase synthesis of substituted benzimidazoles, benzoxazoles and benzothiazoles was developed. Its synthetic utility is exemplified by a structurally diverse set of aromatic heterocycles. Final cleavage is achieved by treatment with sodium methoxide in methanol for 12 h. The corresponding benzimidazoles, benzoxazoles and benzothiazoles were obtained in good isolated yields (22-62%, four steps).     

Zn-K10-clay (clayzic) as an efficient water-tolerant, solid acid catalyst for the synthesis of benzimidazoles and quinoxalines at room temperature

A very simple, green and efficient protocol is developed in which zinc chloride-exchanged K10-montmorillonite (clayzic) is employed as a Lewis acid catalyst in aqueous media at room temperature for the synthesis of various benzimidazoles and quinoxalines from carbonyl compounds and o-phenylenediamine. Among the various catalysts (including claycop and Zn²⁺-Y) studied, clayzic produces benzimidazoles and quinoxalines in higher yield, and with a flexible diamine such as ethylenediamine only the bis-Schiff base is formed. Other salient features of this protocol include milder conditions, atom-economy, absence of coupling agents, and no wastes.     

Zeolite and sulfated zirconia as catalysts for the synthesis of 5-substituted 1H-tetrazoles via [2+3] cycloaddition of nitriles and sodium azide

The [2+3] cycloaddition between various nitriles and sodium azide proceeds smoothly in the presence of zeolite and sulfated zirconia as effective catalysts, in water and DMF/MeOH, to give the corresponding 5-substituted 1H-tetrazoles in good to high yields. The reaction most probably proceeds through the in situ formation of catalyst azide species, followed by a successive [2+3] cycloaddition with the nitriles. This method has the advantages of high yields, simple methodology and easy work-up. The catalyst can be recovered by simple filtration and reused with good yields.     

Nanosized magnesium oxide as catalyst for the rapid and green synthesis of substituted 2-amino-2-chromenes

A nanosized magnesium oxide catalyzed three-component condensation reaction of aldehyde, malononitrile, and α-naphthol proceeded rapidly in water-PEG to afford corresponding 2-amino-2-chromenes in high yields at room temperature. The greener protocol was found to be fairly general and the catalyst was reused in subsequent reactions with consistent activity.     

Lewis acid catalyst free synthesis of benzimidazoles and formamidines in 1,1,1,3,3,3-hexafluoro-2-propanol

A simple, inexpensive, environmentally friendly and efficient route for the synthesis of benzimidazole and formamidine derivatives by the reaction of O-phenylenediamines or amines with orthoesters using hexafluoroisopropanol as a solvent/catalyst is described.     

DBSA mediated chemoselective synthesis of 2-substituted benzimidazoles in aqueous media

An efficient synthetic method has been developed for the facile synthesis of 2-substituted benzimidazoles in organized aqueous media in the presence of a surfactant (viz. DBSA) as catalyst and I₂ as co-catalyst. The method described has the advantages of operational simplicity, excellent yields, high chemoselectivity, and clean and green reaction profile.     

Imidazolium chloride-catalyzed synthesis of benzimidazoles and 2-substituted benzimidazoles from o-phenylenediamines and DMF derivatives

A facile, general, and economical synthesis of diversely functionalized benzimidazoles and 2-substituted benzimidazoles has been realized via the imidazolium chloride-catalyzed cyclization of o-phenylenediamines with DMF derivatives. This protocol shows a broad substrate scope for aliphatic, aromatic, and heteroaromatic amides. A series of benzimidazoles and 2-substituted benzimidazoles have been obtained in moderate to excellent yields.     

Lithium bromide catalyzed solvent free method for synthesis of 2-substituted benzimidazoles and imidazopyridines

<正>The first successful lithium bromide mediated solvent free condensation of arylenediamine and esters to obtain 2-substituted benzimidazole and imidazopyridine in good to excellent yields is described.     

An efficient synthesis of 1,5-benzodiazepine derivatives catalyzed by a solid superacid sulfated zirconia

2,3-Dihydro-1H-1,5-benzodiazepines are synthesized by the condensation of o-phenylendiamine and various ketones in the presence of a versatile solid superacid catalyst ‘sulfated zirconia’ under solvent free conditions.     

Mesoporous silica supported ytterbium as catalyst for synthesis of 1,2‐disubstituted benzimidazoles and 2‐substituted benzimidazoles

The benzimidazole ring is an important pharmacophore in contemporary drug discovery. Thus, effort to identifying new compounds containing benzimidazole scaffolds have gained much attention in recent years. In the present study, MCM‐41 type mesoporous silica with large pore (l‐MSN) supported ytterbium was successfully prepared by wet impregnation method. Among rare earth metal salts, ytterbium triflate has already been widely investigated as a catalyst in organic synthesis but less toxic ytterbium oxide has yet to be explored. Relatively high abundance and low cost of ytterbium with respect to many catalytically active metals (e.g. Pd, Au, Ru, Ir, Pt) offer an opportunity to develop sustainable catalysts for organic conversions. The catalyst has been characterized by various techniques including nitrogen adsorption, FT‐IR, TEM, SEM, EDX technique and elemental mapping. The obtained materials exhibit high surface area and a narrow distribution of mesoporosity. The catalytic performance of the Yb@l–MSNs was tested by synthesis of 1,2‐disubstituted benzimidazoles and 2‐substituted benzimidazoles through the coupling of aldehydes with o‐phenylenediamine. The catalyst resulted in excellent yields in short reaction times and the reaction showed tolerance toward both electron‐donating and electron‐withdrawing functional groups at room temperature. A particularly interesting finding was the solvent selectivity of this reaction; namely, 1,2‐disubstituted benzimidazoles generated as major product in water‐ethanol, while the 2‐substituted benzimidazoles was generated exclusively in non‐polar solvents like toluene.     

Glyoxylic acid as catalyst： A simple selective synthesis of 1,2-disubstituted benzimidazoles in aqueous media

Glyoxylic acid （5 mol%） performs as a novel highly water-soluble catalyst for the synthesis of 2-aryl-l-arylmethyl-lH- benzimidazoles from a wide range of substituted o-phenylenediamines and various substituted aldehydes in good to excellent isolated yields （85-95%） using water as solvent at ambient temperature. The remarkable advantages offered by this method are easily and inexpensive available catalyst, simple procedure, mild conditions, much faster （20--40 rain） reactions and excellent yields of products.     

A simple and efficient one-pot synthesis of β-acetamido carbonyl compounds using sulfated zirconia as a heterogeneous recyclable catalyst

Sulfated zirconia has been employed as an efficient recyclable catalyst for the preparation of various β-acetamidoketones or esters at room temperature. The process involves the one-pot multicomponent reactions of aromatic aldehydes, enolizable ketones or β-ketoesters and acetonitrile in the presence of acetyl chloride.     

An organoantimony nitrate complex with azastibocine framework as water tolerant Lewis acid catalyst for the synthesis of 1,2-disubstitued benzimidazoles

A novel organoantimony complex of 6-cyclohexyl-6,7-dihydrodibenzo[c,f] [1,5]azastibocin-12(5H)-yl nitrate ( 2 ) was synthesized and systematically characterized by techniques such as NMR spectra, TG-DSC, and X-ray diffraction. It was found that the complex 2 exhibits relatively strong Lewis acidity (3.3 < Ho ≤ 4.8) and could be employed as a water tolerant Lewis acid catalyst for the synthesis of synthetically valuable benzimidazole derivatives starting from aldehydes and arylenediamines. This catalytic system shows excellent tolerance toward a wide variety of functional groups, such as methyl, methoxyl, fluoro, chloro, bromo, nitro, cyan, trifluoromethyl, 1-naphthaldehyde, furfural and n-butyl, together with facile reusability in 5 times scale enlarged synthesis.     

One-pot synthesis of 2-substituted quinoxalines using K10-montmorillonite as heterogeneous catalyst

An efficient one-pot synthesis of 2-substituted quinoxalines from 1,2-diamines and phenacyl bromides is developed using K10-montmorillonite (K10 clay) as a catalyst at 50 °C in acetonitrile medium. This method offers an easy route for the synthesis of substituted quinoxalines in high yields. A plausible mechanism is proposed in which quinoxalines are formed via dehydration–dehydrohalogenation–cyclization sequence. Further, the K10 clay catalyst is recovered by simple filtration and reused six times without any loss in its catalytic activity.