ChemInform Abstract: Hydrophobically Directed Aldol Reactions: Polystyrene-Supported L-Proline as a Recyclable Catalyst for Direct Asymmetric Aldol Reactions in the Presence of Water.

A simple synthetic methodology for the preparation of a polystyrene-supported L-proline material is reported, and this material has been used as catalyst in direct asymmetric aldol reactions between several ketones and arylaldehydes to furnish aldol products in high yields and stereoselectivities. Screening of solvents showed that these reactions take place only in the presence of water or methanol, at lower levels of conversion in the latter case. This solvent effect, coupled with the observed high stereoselectivities, has been explained in terms of the formation of a hydrophobic core in the inner surface of the resin, whereas the hydrophilic proline moiety lies at the resin/water interfac…

L-prolinammide supportata su polistirene come organocatalizzatore altamente enantioselettivo nella reazione aldolica diretta

Host—Guest Interactions Involving Cyclodextrins: Useful Complementary Insights Achieved by Polarimetry.

Abstract By means of simple polarimetry, we studied the binding abilities of native α-, β-, and γ-cyclodextrins toward a group of suitably chosen model guests. We were able to get reliable estimations of the binding constants K, spread over a wide range (from 3.7 to 12,300 M−1), allowing us to carry on interesting comparisons. A comprehensive discussion of polarimetric data, and in particular a detailed analysis of the variations ΔΘ of molar optical activities consequent to inclusion, offered us the opportunity to get useful insights into the structure and dynamic behavior of host–guest complexes.

Can the absence of solvation of neutral reagents by ionic liquids be responsible for the high reactivity in base-assisted intramolecular nucleophilic substitutions in these solvents?

[reaction: see text] The kinetics of the rearrangement of the Z-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole (1a) into the relevant 4-benzoylamino-2,5-diphenyl-1,2,3-triazole (2a) induced by amines have been studied in two room-temperature ionic liquids (IL-1, [BMIM][BF4] and IL-2, [BMIM][PF6]). The data collected show that the reaction occurs faster in ionic liquids than in other conventional solvents previously studied (both polar or apolar, protic or aprotic). Presumably, this could depend on their peculiar ability to minimize the strong substrate-solvent, amine-solvent and amine-amine interactions occurring in conventional solvents.

Mononuclear rearrangement of heterocycles in ionic liquids catalyzed by copper(II) salts

Abstract The reactivity of E- and Z-phenylhydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazole in the presence of CuCl2 and Cu(ClO4)2·6H2O has been studied in four imidazolium ionic liquids [bmim][X] (X=BF4−, PF6−, SbF6− and CF3SO3−). The reaction may follow different mechanistic patterns, depending on the nature of the ionic liquid anion, accounting for both qualitative and kinetic data. In the presence of CuCl2, two processes take place at the same time, i.e., the E⇆Z isomerization and the rearrangement of Z-isomer into the relevant 4-benzoylamino-2,5-diphenyl-1,2,3-triazole. In contrast, in the presence of Cu(ClO4)2·6H2O, the rearrangement occurs only in solution of [bmim][BF4] and [bmim][C…

The effect of the cation p-surface area on the 3D organization and catalytic ability of imidazolium-based ionic liquids

The dichotomic nature of ionic liquids (ILs, simple solvents or supramolecular fluids) induced us to carry out a structural investigation of some mono-and dicationic ionic liquids using 1D and 2D NMR, resonance light scattering, and UV/Vis spectroscopy. Ionic liquids with different cation π-surface areas were used, namely [bmim][NTf2], [Bzmim][NTf 2], [Bzbim][NTf2], [p-Xyl-(bim)2][NTf 2]2, and [m-Xyl-(bim)2][NTf2] 2 [bmim = 1-butyl-3-methylimidazolium, Bzmim = 1-benzyl-3- methylimidazolium, Bzbim = 1-benzyl-3-butylimidazolium, NTf2 = bis(trifluoromethansulfonyl)imide]. In order to verify to what extent the structural investigation, coupled with the determination of solvent parameters, could…

Design of PNIPAAM covalently grafted on halloysite nanotubes as a support for metal-based catalysts

A thermo-responsive polymer such as poly(N-isopropylacrylamide) (PNIPAAM) was covalently grafted on the external surface of halloysite nanotubes (HNTs) by means of microwave irradiation. This nanomaterial was used as a support and stabilizer for palladium nanoparticles. The obtained HNT–PNIPAAM/PdNPs was characterized by means of TGA, SEM, EDS and TEM analyses. The palladium content of the catalyst was estimated to be 0.4 wt%. The stability of the catalytic material at different temperatures (below and above the PNIPAAM lower critical solution temperature) was tested in the Suzuki reaction under microwave irradiation. In addition, TEM analysis after five consecutive runs was performed. The …

Task Specific Dicationic Ionic Liquids: Recyclable Reaction Media for the Mononuclear Rearrangement of Heterocycles

Nine functionalized dicationic ionic liquids were used to study the base catalyzed mononuclear rearrangement of (Z)-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole into the corresponding triazole at 363 K. Ionic liquids were characterized by the presence of 1-(1-imidazolylmethyl)-3,5-di[1-(3'-octylimidazolylmethyl)]benzene cation, bearing on the structure a neutral imidazole unit as basic functionality. Besides anions generally used for monocationic ionic liquids, such as [Br(-)], [BF4(-)], and [NTf2(-)], also dianions having a rigid aromatic spacer such as 1,4-benzenedicarboxylate, 2,6-naphthalenedicarboxylate, and 1,5- and 2,6-naphthalenedisulfonate were taken into account. Further…

A joint experimental and ab initio study on the reactivity of several hydroxy selenides. Stereoselective synthesis of cis-disubstituted tetrahydrofurans via seleniranium ions

Abstract The reactivity of several hydroxy selenides bearing an ethereal chain with catalytic amounts of perchloric acid in dichloromethane was investigated. Results showed that the position of the oxygen atom with respect to the seleniranium ring was crucial in order to get a good yield of the cyclized product. The factors on which yields of the 5- endo cyclization of the seleniranium ions depend were analysed by ab initio (HF/3-21G ∗ ) studies. An explanation of the different coordinating ability, towards the positively charged selenium atom, of the allylic OMe and homoallylic OH-2 groups was given.

Low-loading asymmetric organocatalysis

Asymmetric organocatalysis is now recognized as the third pillar of asymmetric synthesis. Recent years have witnessed increasing interest towards the use of highly active and stereoselective organocatalysts. This critical review documents the advances in the development of chiral organocatalysts which are systematically used in ≤3 mol% loading in all the sub-areas of the field, namely aminocatalysis, Brønsted acids and bases, Lewis acids and bases, hydrogen bond-mediated catalysis, phase transfer and N-heterocyclic carbene catalyses (194 references).

Novel Hydroxyproline-derivatives as powerful aldolase-I mimics

MICROWAVE-ASSISTED FUNCTIONALIZATION OF HALLOYSITE NANOTUBE SURFACE

Halloysite, Al2Si2O5·2H2O, is a naturally occurring two-layered alluminosilicate, chemically similar to kaolin, which has a predominantly high-aspect-ratio hollow tubular structure in the submicrometer range and an internal diameter in the nanometer range. The size of halloysite nanotubes (HNTs), generally varies from 50 to 70 nm in external diameter, ca. 15 nm diameter lumen, and 0.5 to 1 μm in length. Halloysite tubes have aluminol (Al-OH) groups on the internal surface and siloxan groups (Si-O-Si) on the external surface. The very large diameter of the halloysite lumen makes it potentially suitable for the accommodation of a range of guests. In recent reports, for example, the mesoporous…

Co-loaded cardanol/triazole-halloysite system: characterization of the supramolecular complex and evaluation of its antiproliferative activity

Halloysite nanotubes modified with triazolium salts (f-HNT) were found to be promising drug carriers for biological molecules [1 ]. In this work we report data about f-HNT as carrier for cardanol, a molecule with interesting biological activity [2]. The interactio n between cardanol and f- HNT was highlighted by HPLC, FTIR spectroscopy, TGA , water contact angle measurements and SEM investigations. Release of cardanol from the system and cytotoxic e ffect of the complex f- HNT/Card on hepatocarcinoma cell lines were, also, evaluated. The obtained results put forward the use of halloysite as drug c arrier

Recyclable Organocatalysts in Asymmetric Reactions

Diastereoselective synthesis of substituted 2-phenyltetrahydropyrans as useful precursors of aryl C-glycosides via selenoetherification

The cyclization of several substituted 5-phenyl-pent-4-en-1-ols with selenium electrophiles along some mechanistic considerations is discussed. In particular, an efficient diastereoselective synthesis of a 2,3,5,6-tetrasubstitued tetrahydropyran is reported. These findings open an interesting approach: the use of chiral selenium electrophiles for cyclization of chiral substrates. The cyclized products are useful starting material for the synthesis of D- or L-aryl C-glycosides.

Lipase-catalyzed resolution of anti-6-substituted 1,3-dioxepan-5-ols

Abstract Several anti-6-substituted 1,3-dioxepan-5-ols were kinetically resolved using an immobilized lipase (Amano PS–C II) in toluene in the presence of vinyl acetate at 30 °C. This approach provided, in some cases, the alcohol and the acetate in high enantiomeric purity, depending on the nature of the substituent (R = N3, SePh, I, OBn) and the acetal group (unsubstituted or dimethyl). The role of the size of substituents is also discussed. Enantiopure anti-6-substituted 1,3-dioxepan-5-ols are useful building blocks.

Properties and Structural Studies of Multi-Wall Carbon Nanotubes-Phosphate Ester Hybrids

Long chain phosphate esters bearing at least one or two aryl groups have been synthesized and used for the preparation of stable multi-walled carbon nanotube (MWCNT) hybrids. The non-covalent interaction ester/MWCNT has been investigated by several techniques (SEM, UV-vis, 31P-NMR, RAMAN). The used phosphate ester derivatives demonstrated the ability to produce an excellent dispersion of MWCNT in CHCl3. The obtained dispersions showed a great stability from one to at least three weeks in the range of concentration considered. Thermal analysis showed an increase in the decomposition temperature for the hybrids with respect to pristine MWCNT.

Green conditions for the Suzuki reaction using microwave irradiation and a new HNT- supported ionic liquid-like phase (HNT-SILLP) catalyst

A new catalytic system based on modified halloysite nanotubes was employed in the Suzuki reaction under microwave irradi- ation. A set of solvents, times and bases was screened and the best experimental conditions were obtained when the reactions were carried out for 10 min in water–ethanol at 120 °C in presence of K2CO3 as base. Good recyclability was observed. The new catalytic system was employed using either 1 mol% or 0.1 mol%. The palladium catalyst displayed good activity, allowing the synthesis of several biphenyl compounds in high yield working with only 0.1 mol% palladium loading. The application of mi- crowave irradiation decreased the reaction time and also improved conversion wi…

Supported ionic liquid asymmetric cathalysis. A new method for chiral catalyst recycling

A new method for chiral catalysts recycling, based on the supported ionic liquid asymmetric catalysis concept, has been developed. This concept involves the treatment of a monolayer of covalently attached ionic liquid on the surface of silica gel with additional ionic liquid. These layers serve as the reaction phase in which the homogeneous chiral catalyst is dissolved. As first application of this concept the L-proline-catalyzed aldol reaction has been carried out. Good yields and ee values, comparable with those obtained under homogeneous conditions have been obtained. Moreover, this material shows high regenerability.

Amine basicity: measurements of ion pair stability in ionic liquid media

Abstract The stability constants relevant to the formation of amine/p-nitrophenol ion pairs have been determined in [bmim][BF4] solution, in the presence of butylamine, piperidine, and triethylamine, by using spectrophotometric measurements. In order to evaluate how the ion pair stability is affected by ionic liquid structure, piperidine has been chosen as model amine for studies in [bmim][PF6], [bmim][NTf2], [bm2im][NTf2] and in several [bmim][BF4]/1,4-dioxane binary mixtures. Data obtained in ionic liquid solutions have been compared with those previously reported in conventional organic solvents.

ChemInform Abstract: Substituent Effect on Oxidative Cyclization of Aldehyde Thiosemicarbazones with Ferric Chloride.

The reactivity of aldehyde thiosemicarbazones 1 with ferric chloride solutions was examined. When compounds 1 are not substituted on the N-2 nitrogen atom formation of 1,3,4-thiadiazole 3 heterocyclic ring was observed. In contrast 1,2,4-triazoline 4 and/or 1,3,4-thiadiazoline 5 heterocyclic rings were afforded when N-2 nitrogen atom carried a methyl or a phenyl group. The reaction mechanism is also discussed.

Molecular “Pincer” from a Diimidazolium Salt: A Study of Binding Ability

The anion recognition ability of the dicationic imidazolium salt 3,3′-di-n-octyl-1,1′- (1,3-phenylenedimethylene)diimidazolium 1,5-naphthalenedisulfonate ([m-Xyl-(oim)2][1,5-NDS]) was investigated in acetonitrile solution by means of proton NMR titrations. A wide range of anions, comprising simple inorganic ions, halides, and mono- and dicarboxylates was taken into account. The study showed that this receptor binds carboxylate anions more strongly than halides. Moreover [m- Xyl-(oim)2][1,5-NDS] displays selectivity for di- over monocarboxylate anions. The complex stability was mainly affected by the anion basicity in the presence of monocarboxylates, whereas the flexibility of the alkyl cha…

Abilità organizzante di liquidi ionici: effetto sulla velocità di reazioni di trasposizione mononucleare di eterocicli.

Recyclable Chiral Imidazolidinone Catalyst for α-Alkylation of Aldehydes

Fluorescent naphthalimide-imidazolium hydrogels for biomedical applications

Bioimaging and in vivo imaging are cornerstone technologies in support of biomedical diagnosis. However, in some cases imaging methods have increased cancer risks for patients. Moreover, the most widely used diagnostic medical imaging technique, X-ray imaging, is the largest man-made source of radiation exposure to the general population. Thus, the research of new efficient and less invasive materials for imaging is quite urgent. Supramolecular hydrogels have recently proved to be promising biological carriers to load versatile bioimaging agents for in vitro or in vivo bioimaging, thanks to the ability to undergo reversible swelling and gel–sol transition in response to various physiologica…

Ciclodestrine borate. Sintesi, acidità e attività catalitica

Binding properties of mono-(6-deoxy-6-amino)-β-cyclodextrin towards p-nitroaniline derivatives: a polarimetric study

Abstract Polarimetry was used in order to investigate the formation of supramolecular complexes between mono-6-amino-β-cyclodextrin and various p-nitroaniline derivatives at two different pH values. Comparison with the behaviour of native β-cyclodextrin gave us the opportunity to consider the effect exerted by the presence of charged groups, having different solvation requirements, on the binding equilibrium. Data offer some support to the hypothesis of ‘dynamic co-inclusion’ of solvent molecules within the host–guest complex.

ChemInform Abstract: New Ionic Liquid-Modified Silica Gels as Recyclable Materials for L-Proline- or H-Pro-Pro-Asp-NH2-Catalyzed Aldol Reaction.

L-proline and the tripeptide H–Pro–Pro–Asp–NH2 (1) have been supported, by adsorption, onto the surface of modified silica gels functionalized with a monolayer of covalently attached 1,2-dimethyl-imidazolium chloride, tetrafluoroborate or hexafluorophosphate ionic moieties, respectively. Three different linkers were used to attach the ionic liquid moiety to the surface of these supports. The resulting materials have been used as catalysts for the aldol reaction between acetone and several substituted benzaldehydes. Good yields and enantioselectivities, comparable to or better than those obtained under homogeneous conditions, were obtained. These materials are easily recovered by filtration,…

ChemInform Abstract: Green Conditions for the Suzuki Reaction Using Microwave Irradiation and a New HNT-Supported Ionic Liquid-Like Phase (HNT-SILLP) Catalyst.

Aryl iodides are coupled with conversions comparable to aryl bromides whereas conversions of aryl chlorides are significantly lower.

Past, Present and Future Perspectives on Halloysite Clay Minerals

Halloysite nanotubes (HNTs), clay minerals belonging to the kaolin groups, are emerging nanomaterials which have attracted the attention of the scientific community due to their interesting features, such as low-cost, availability and biocompatibility. In addition, their large surface area and tubular structure have led to HNTs’ application in different industrial purposes. This review reports a comprehensive overview of the historical background of HNT utilization in the last 20 years. In particular it will focus on the functionalization of the surfaces, both supramolecular and covalent, following applications in several fields, including biomedicine, environmental science and catalysis.

Polyaminocyclodextrin nanosponges: synthesis, characterization and pH-responsive sequestration abilities

New pH-responsive nanosponges were obtained by reacting four different polyaminocyclodextrins with heptakis-(6-bromo)-(6-deoxy)-β-cyclodextrin. The materials obtained were characterized by various techniques (FT-IR, potentiometric titration, differential scanning calorimetry (DSC), porosimetry (BET), 13C{1H} CP-MAS NMR). Their adsorption abilities at different pH values were verified towards a suitable set of model guests, and seem mainly controlled by electrostatic interactions, as a function of the protonation/charge status of the polymer matrix. By contrast, data positively point out a lesser importance assumed by the induced-fit effect, important in affecting the formation of host–guest…

Geminal Imidazolium Salts: A new Class of Gelators

The gelling behavior of some geminal diimidazolium salts was investigated in solvents differing in polarity and hydrogen bond donor ability. The used salts, namely the 3,3'-di-n-decyl-1,1'(1,4-phenylenedimethylene)diimidazolium dibromide [p-Xyl-(decim)(2)][Br](2) (1), the 3,3'-di-n-dodecyl-1,1'(1,4-phenylenedimethylene)diimidazolium dibromide [p-Xyl-(dodecim)(2)][Br](2) (2), and the 3,3'-di-n-dodecyl-1,1'(1,4-phenylenedimethylene)diimidazolium ditetrafluoroborate [p-Xyl-(dodecim)(2)][BF(4)](2) (3), differ in the alkyl chain length and in the anion properties, such as size, shape, and coordination ability. In all cases in which gelation process was observed, the obtained gels were characteri…

Dual drug-loaded halloysite hybrid-based glycocluster for sustained release of hydrophobic molecules

A dual drug-loaded HNT–CD glycocluster delivery system based on halloysite nanotubes and carbohydrate functionalized cyclodextrin was developed by a green protocol using solvent-free microwave irradiation. The nanohybrid was employed for concurrent load and release of silibinin and curcumin. The new delivery system was characterized by means of TGA, FT-IR spectroscopy, SEM and DLS. These techniques confirm the successful loading of the two drugs in the system. SEM and DLS measurements highlighted that the nanomaterial preserves a tubular structure with an average hydrodynamic radius of ca. 200 nm. The release of the drugs from the HNT glycocluster was investigated by means of UV-vis spectro…

Cyclodextrins: heterocyclic molecules able to perform chiral recognition (Part II)

The present paper collects the most significant advances appeared since late 1998 up to June 2005 in the field of applications of natural and modified cyclodextrins as chiral selectors, with particular regard for pharmaceuticals and natural products.

Ecocompatible Halloysite/Cucurbit[8]uril Hybrid as Efficient Nanosponge for Pollutants Removal

Hybrid materials based on halloysite nanotubes (HNT) and cucurbit[8]uril (CB[8]) were prepared with the aim to obtain efficient nanosponges towards hydrocarbons both in liquid and vapor phases. The loading on both HNT surfaces and the hybrid morphology were evidenced by FTIR spectroscopy, thermogravimetric analysis and scanning electron microscopy. In order to highlight the interactions in the hybrid 13C {1H} CP-MAS NMR experiments were performed. The aqueous colloidal stability of HNT/CB[8] was highlighted through ζ potential and dynamic light scattering measurements. The HNT/CB[8] composite was employed as nanosponge to capture aromatic oils in aqueous phase as evidenced by fluorescence e…

Stereoselective aldol reaction catalyzed by a highly recyclable polystyrene supported substituted prolinamide catalyst

Polystyrene supported substituted prolinamide was used as catalyst in the aldol reaction between cyclohexanone or acetone and several substituted benzaldehydes in chloroform/water. This catalyst afforded aldol products in high yields and stereoselectivities, especially in the case of reactions performed with acetone. The catalyst was easily recovered by filtration and reused, after regeneration with formic acid, up to 22 times.

Functionalised Imidazolium Dicationic Ionic Liquids used as reaction media for base catalyzed organic reactions

The effects of structural changes on the anti-microbial and anti-proliferative activities of diimidazolium salts

An array of diimidazolium salts has been synthesized and used to investigate their anti-microbial and anti-proliferative activities. In particular, salts based on the 3,30-di-n-alkyl-1,10-(1,n-phenylenedimethylene)- diimidazolium cation and differing in the alkyl chain length on the imidazolium ion, the isomeric substitution on the aromatic spacer and in the anion nature were used. The anti-proliferative activity was evaluated against cervical (HeLa), colon adenocarcinoma (HT-29) and breast (SKBR3) cancer cell lines. In the latter case, also a morphological assessment after treatment with salts was performed. All salts were tested for their hemolytic activity against human erythrocytes. On …

Prolinamide-Supported Polystyrene: a Novel Highly Recyclable Organocatalyst for the Asymmetric Aldol Reaction

Host-guest interactions between DMpillar[5]arene and fluorescent imidazolium salts

ChemInform Abstract: Asymmetric Synthesis Using Polymer-Immobilized Proline Derivatives

Determinazione di costanti di formazione di coppie ioniche in liquidi ionici

SYNTHESIS AND CHARACTERIZATION BY THERMOGRAVIMETRIC ANALYSIS OF A NEW DRUG DELIVERY SYSTEM BASED ON HALLOYSITE NANOTUBES

Two-Component Hydrogels Formed by Cyclodextrins and Dicationic Imidazolium Salts

In the framework of our recent interest in studying the gelling behaviour of imidazolium salts, we took into account the possibility of obtaining two-component hydrogels by combining cyclodextrins and dicationic imidazolium salts. In particular, we used diimidazolium salts differing in the alkyl chain length and in the size, shape, and coordination ability of the anion, namely the 3,3′-di-n-decyl- and 3,3′-di-n-dodecyl-1,1′-(1,4-phenylenedimethylene)diimidazolium dibromide, and 3,3′-di-n-dodecyl-1,1′-(1,4-phenylenedimethylene)diimidazolium ditetrafluoroborate and dihexafluorophosphate. As far as cyclodextrins are concerned, to gain information on the effects of different sized cyclic oligos…

Insights into the Formation and Structures of Molecular Gels by Diimidazolium Salt Gelators in Ionic Liquids or “Normal” Solvents

Insights are provided into the properties of molecular gels formed by diimidazolium salts both in “normal” solvents and ionic liquids. These materials can be interesting for applications in green and sustainable chemistry in which ionic liquids play a significant role, like catalysis and energy. In particular, two positional isomers of a diimidazolium cation have been examined with a wide range of anions for their ability to form gel phases. In particular, di-, tri-, and tetravalent anions bearing aliphatic or aromatic spacers were paired with the divalent cations. The properties of the organo- and ionogels formed have been analyzed by means of several different techniques, including calori…

Ionic Liquids Binary Mixtures: Promising Reaction Media for Carbohydrates Conversion in 5-HMF

L-prolina supportata su polistirene: un versatile organocatalizzatore eterogeneo

Polarimetric study of binding equilibria between cyclodextrins and some suitable organic guests

Anion and ionic liquid effects on ionogel phases formation

Geminal organic salts have been recently introduced as the third generation of ionic liquids.1 Like their monocationic precursors they generally show high thermal stability and low corrosiveness, as well as high polarity and structural order degree.2 All these features make them good candidates to be used in the formation of conductive gel phases, that afterwards may find application as organized reaction media or in the preparation of dye sensitized solar cells.3 In this context, we have recently synthesized some task specific geminal organic salts and investigated their behaviour as gelators. The obtained salts were able to gel ionic liquid solutions. In order to have information about th…

Supported Organocatalysts: a Powerful Tool in Organic Synthesis

Functionalized halloysite nanotubes: Efficient carrier systems for antifungine drugs

Abstract Halloysite-cyclodextrin hybrid was employed as carrier for sustained release of clotrimazole for vaginal or buccal treatment of Candidiasis. The nanocarrier was obtained by functionalization of halloysite surface with cyclodextrin moieties by means of microwave irradiation, with the final goal to obtain a scaffold for the covalent linkage of cysteamine hydrochloride. The interaction between clotrimazole and the pristine components, namely cyclodextrin and halloysite, was thoroughly investigated by several techniques such as DSC, TGA, UV–vis spectroscopy and some adsorption studies were, also, carried out. The release of the antifungine molecule was finally investigated in a medium …

Supported Ionic Liquid Asymmetric Catalysis. A New Method for Chiral Catalysts Recycling. The Case of Proline-Catalyzed Aldol Reaction.

A new method for chiral catalysts recycling, based on the supported ionic liquid asymmetric catalysis concept, has been developed. This concept involves the treatment of a monolayer of covalently attached ionic liquid on the surface of silica gel with additional ionic liquid. These layers serve as the reaction phase in which the homogeneous chiral catalyst is dissolved. As first application of this concept the L-proline-catalyzed aldol reaction has been carried out. Good yields and ee values, comparable with those obtained under homogeneous conditions have been obtained. Moreover, this material shows high regenerability.

Halloysite nanotubes: a green resource for materials and life sciences

Clay minerals are considered one of the materials of the 20th century for their peculiar physico-chemical features. Among them, halloysite nanotubes (HNTs) are an emerging nanomaterial with a particular tubular structure that makes them a low cost and valuable alternative to the most common carbon nanotubes. Due to their tubular morphology, HNTs are employed in several fields acting as nanocontainers for different compounds for applications in drug carrier and delivery fields, catalysis, and as filler for polymeric matrices. The modification of HNTs’ surfaces allows to the synthesis of different nanoarchitectures that can improve the mechanical and thermal performance of polymer as well as …

Hydrophobically directed aldol reactions: polystyrene-supported L-proline as a recyclable catalyst for direct asymmetric aldol reactions in the presence of water

A simple synthetic methodology for the preparation of a polystyrene- supported L-proline material is reported, and this material has been used as catalyst in direct asymmetric aldol reactions between several ketones and arylaldehydes to furnish aldol products in high yields and stereoselectivities. Screening of solvents showed that these reactions take place only in the presence of water or methanol, at lower levels of conversion in the latter case. This solvent effect, coupled with the observed high stereoselectivities, has been ex- Introduction In the last decade organocatalysis has became a field of great interest.[1] Organocatalysts are metal-free small organic molecules that are able t…

Two component chiral gels: a study of properties and behavior as recognition systems

Oxidative degradation properties of Co-based catalysts in presence of ozone

Crystal structure and reactivity of 2-chloro-3,5-dinitrothiophene and of 2-phenylsulphonyl-3,5-dinitrothiophene with nucleophiles

The geometry obtained by a crystal structure determination of the title compounds, as compared with that of the analogous benzene derivatives, along with results of ab initio calculations, is used to interpret the different SNAr reactivities in some thiophene and benzene compounds. The smaller rotation of the nitro groups with respect to the aromatic rings observed in thiophene derivatives should be considered a relevant factor in the higher reactivity in the thiophene series.

Pharmaceutical properties of supramolecular assembly of co-loaded cardanol/triazole-halloysite systems

Halloysite nanotubes were explored as drug carrier for cardanol, which is considered as a promising natural anticancer active species. To this aim, besides the pristine nanoclay, a chemical modification of the nanocarrier was performed by attaching triazolium salts with different hydrophobicity at the outer surface of the hollow nanotubes. The interaction between cardanol and nanotubes was highlighted in solution by HPLC. This method proved the loading of the drug into the nanotubes. The solid dried complexes formed by pristine and modified halloysite with the cardanol were characterized by IR spectroscopy, thermogravimetric analysis as well as water contact angle to evidence the structure,…

A quantitative study of substituent effects on oxidative cyclization of some 2-methylsubstituted aldehydes. Thiosemicarbazones induced by ferric chloride

In order to gain further mechanistical information about the cyclization of thiosemicarbazones and thiosemicarbazone-type substrates induced by metallic salts as oxidizing agents, we performed the synthesis of substrates 1a-s and a kinetic study of the oxidative cyclization of 1 to 5-imino-Δ2-1,3,4-thiadiazole 2 and 1,2,4-triazoline-5-thione 3 derivatives induced by methanolic ferric chloride solutions. The results of cyclization were compared to those of corresponding semicarbazones. The kinetic data were analyzed by means of the Hammett's equation and ρ values discussed.

Protonazione del p-nitrofenato di sodio in liquidi ionici: una "sonda" per la determinazione della forza acida

Palladium supported on Halloysite-triazolium salts as catalyst for ligand free Suzuki cross-coupling in water under microwave irradiation

Abstract Environmental friendly halloysite-dicationic triazolium salts (second generation) obtained by subsequent click reactions of a diyne derivative in the presence of 2-azidopropyl-modified halloysite nanotubes, were used as supports for palladium catalyst. Thanks to the high triazolium loading (25%) these materials were able to support higher amount of the metal than that on the monocationic derivative (first generation). Such materials were characterized by thermogravimetric analysis, FT-IR spectroscopy and SEM investigations. The new catalytic system was employed in the ligand free Suzuki cross-coupling under microwave irradiation. A set of solvent, time and% loading of palladium was…

A competitive reactivity study on the oxidative cyclization of thiosemicarbazones into 1,3,4-thiadiazoles

Abstract In order to obtain useful insights on the mechanism of formation of 2(3H)-imino-1,3,4-thiadiazoles by oxidative cyclization of aldehyde thiosemicarbazones with Cu(II) or Fe(III) salts, a competitive reactivity study was performed on a suitable set of diversely substituted substrates, by means of HPLC techniques. This approach enabled to exploit Hammett’s equation without performing otherwise difficult-to-run kinetic experiments. The results presented herein support the hypothesis that the formation of the thiadiazole ring is induced by the attack of the oxidizing Lewis acid metal cation onto the imine-like nitrogen atom of the thiosemicarbazone substrate. Beyond mechanistic interpr…

Multicavity halloysite-amphiphilic cyclodextrin hybrids for co-delivery of natural drugs into thyroid cancer cells

Multicavity halloysite nanotube materials were employed as simultaneous carriers for two different natural drugs, silibinin and quercetin, at 6.1% and 2.2% drug loadings, respectively. The materials were obtained by grafting functionalized amphiphilic cyclodextrin onto the HNT external surface. The new materials were characterized by FT-IR spectroscopy, SEM, thermogravimetry, turbidimetry, dynamic light scattering and ζ-potential techniques. The interaction of the two molecules with the carrier was studied by HPLC measurements and fluorescence spectroscopy, respectively. The release of the drugs from HNT-amphiphilic cyclodextrin, at two different pH values, was also investigated by means of…

Asymmetric Aldol Reaction with Polystyrene-Supported Proline-Based Catalysts

Supramolecular Hydro- and Ionogels: A Study of Their Properties and Antibacterial Activity.

Diimidazolium-based organic salts, bearing peptides or amino acids as anions have been synthesised and tested for their gelling ability in biocompatible solvents. These low molecular weight salts were successfully used as gelators in phosphate buffered saline (PBS) solution and ionic liquids. Then, the properties of the obtained soft materials were analysed in terms of melting temperature and gel strength as accounted for by rheological investigations. The gel-phase formation was studied by using UV/Vis and resonance light scattering measurements, whereas the morphology of the soft materials was analysed by using polarised optical microscopy and scanning electron microscopy. To get informat…

L-Prolina supportata su polistirene: un versatile catalizzatore eterogeneo

Synthesis, characterization and antimicrobial activity of polyaminocyclodextrin-capped Ag Nanoparticles

Biocompatible Ag nanocomposites were prepared by photoreduction of ammoniacal silver acetate in the presence of a polyaminocyclodextrin, namely the poly-{6-[3-(2-(3-aminopropylamino)-ethylamino)-propylamino]}-(6-deoxy)-b-CD (amCD, figure 1). The obtained Ag-amCD systems, which possess an oniontype structure [1] with a metal core surrounded by several layers of the capping agent, were characterized by means of various complementary techniques. In particular, FT-IR spectroscopy confirmed the presence of the amCD scaffold in the composite, and evidenced a partial oxidative degradation of the polyamine branches,due to the fact that these groups function as sacrificial reducing agents in the pho…

Synthesis and Characterization of Halloysite-Cyclodextrin Nanosponges for Enhanced Dyes Adsorption

Inorganic-organic nanosponge hybrids based on halloysite clay and organic cyclodextrin derivatives (HNT-CDs) were developed by means of microwave irradiations in solvent-free conditions. The HNT-CDs nanomaterials characterized by FT-IR, TGA, BET, TEM, SEM, DLS, and zeta-potential have showed a hyper-reticulated network which possesses both HNT and cyclodextrin peculiarities. The new HNT-CDs nanosponge hybrids were employed as nanoadsorbents, first choosing Rhodamine B as the dye model, and furthermore for the removal of some cationic and anionic dyes, under different pH values (1.0, 4.54, and 7.4). The collected results showed that the pH solution as well as the electrostatic interactions a…

A study of the behaviour of 2,4-substituted thiosemicarbazides toward orthoesters: Formation of mesoionic compounds

The reactions beetwen 2,4-disubstituted thiosemicarbazides and orthoesters in refluxing xylene led to the formation of the 1,2,4-triazoline-5-thione ring and to the 1,2,4-triazolium-5-thiolate ring. The formation of the mesoionic componds is due to rearrangement of the easily available 2,4-disubstituted thiosemicarbazides to 1,4-disubstituted thiosemicarbazides under the reaction conditions adopted. This method can be usefully used for the synthesis of mesoionic compounds, especially in the case of the 2-methyl-4-phenylthiosemicarbazide.

Recyclable Heterogeneous and Low-Loading Homogeneous Chiral Imidazolidinone Catalysts for α-Alkylation of Aldehydes

Two polystyrene-supported and six homogeneous MacMillan imidazolidinone catalysts were prepared and tested for the asymmetric α-alkylation of propanal with benzodithiolylium tetrafluoroborate. The chiral imidazolidinone was linked to polystyrene through the N-3 atom or through the phenyl ring and their catalytic activity was compared with that of their unsupported precursors. This comparison has allowed us to find an unsupported catalyst that displays high catalytic activity down to 5 or 2 mol % at room temperature with a high level of enantioselectivity also when used with hexanal and 3-phenylpropanal. In addition, one of the heterogeneous materials was revealed to be highly recyclable for…

Sistemi TEMPO-C60 come Catalizzatori Riciclabili Attivi nell’Ossidazione di Alcoli

GREEN CONDITIONS FOR THE SUZUKI REACTIONS BY USING MICROWAVE IRRADIATION AND MODIFIED HALLOYSITE/Pd CATALYST

Halloysite nanotube (HNT) is an emerging biocompatible material with appealing perspective for technological applications, such as in catalysis1 and in pharmaceutical research.2 Halloysite is a double-layered aluminosilicate mineral that has a predominantly hollow tubular structure. The functionalization of HNTs is a good strategy to introduce an organic moiety onto the external surface and, therefore, to obtain innovative catalyst supports.3 We have modified the external surface of halloysite nanotube with octylimidazolium moieties (HNT-IL) by microwave irradiation in solvent-free conditions and we have have employed this material as support catalyst of Pd nanoparticles. The new HNT/Pd cat…

p-Nitrophenolate: A Probe for Determining Acid Strength in Ionic Liquids

In order to obtain an acidity scale in room-temperature ionic liquid solutions, the protonation equilibrium of sodium p-nitrophenolate in [bm(2)im][NTf(2)] and in [bmpyrr][NTf(2)], at 298 K, has been studied by means of spectrophotometric titration. Carboxylic acids differing in both structure and in water solution strength have been used. Data collected indicate that in the analyzed ionic liquid solutions carboxylic acids are less dissociated than in water solution. Furthermore, by virtue of a mutual interaction, the studied equilibrium seems to be affected by both the nature of the ionic liquids and the carboxylic acids.

STABILITY AND ORGANOCATALYTIC EFFICIENCY OF N-HETEROCYCLIC CARBENES ELECTROGENERATED IN ORGANIC SOLVENTS FROM IMIDAZOLIUM IONIC LIQUIDS

The kinetic of degradation of 1-butyl-3-methylimidazole-2-ylidene (selected as model N-heterocyclic carbene - NHC), generated in organic solvents by cathodic reduction of the parent 1-butyl-3- methylimidazolium salts BMIm-X, was studied by a simple voltammetric analysis. The effect of NHC degradation rate on the efficiency of an organocatalyzed reaction (the synthesis of g-butyrolactone from cinnamaldehyde and trifluoromethylacetophenone) was investigated. The nature of the solvent and of the anion X have a remarkable effect on the stability of the NHC, the bis(trifluoromethylsulfonyl) imide anion being the best for a long lasting carbene (while acetonitrile seems to be the worst solvent). …

Two components organogels as molecular recognition systems: properties, behavior and future applications

Functionalised diimidazolium salts: the anion effect on the catalytic ability

The catalytic ability of some functionalised diimidazolium ionic liquids was tested using the Michael addition of malononitrile to t-chalcone as probe reaction. Diimidazolium salts characterized by the presence of 1-(1-imidazolylmethyl)-3,5-di-[1-(3-octylimidazolylmethyl)]benzene cation and differing in the anion structure were used. Both mono- and dianions were employed and among these some chiral anions generally used as organocatalysts were taken into account. Data collected were analysed both as function of ionic liquids structure and basicity, evaluated using the Hammett basicity function. Although the use of chiral anions did not allow performing a stereochemical control of the reacti…

SALI ORGANICI: “TECTONI” PER LO STUDIO DI PROCESSI DI SELF-ASSEMBLY IN SOLVENTI ORGANICI

Studio dell’interazione Im-Eu-X: nuovi leganti ecocompatibili per l’Europio

ChemInform Abstract: Novel Prolinamide-Supported Polystyrene as Highly Stereoselective and Recyclable Organocatalyst for the Aldol Reaction.

A new prolinamide derivative anchored to a polystyrene support has been straightforwardly prepared and employed as heterogeneous catalyst in the direct asymmetric aldol reaction with good results in terms of yield and stereoselectivity. The optimal reaction conditions were found when a 1:2 (v/v) water/chloroform mixture was used. This mixture was the best compromise between the good swelling properties of chloroform and the formation of a concentrated organic phase due to the presence of water. Noticeably, the enantioselectivities obtained employing acetone as ketone were, to the best of our knowledge, the highest achieved with a supported proline derivative. This catalyst can be easily rec…

Supported ionic liquids. New recyclable materials for L-proline-catalyzed aldol reaction

Effect of ionic liquid organizing ability and amine structure on the rate and mechanism of base induced elimination of 1,1,1-tribromo-2,2-bis(phenyl-substituted)ethanes

Abstract The kinetics of the elimination reaction of 1,1,1-tribromo-2,2-bis(phenyl-substituted)ethanes into the corresponding 1,1-dibromo-2,2-bis(phenyl-substituted)ethenes induced by amines were studied in three room temperature ionic liquids ([BMIM][BF 4 ], [BMIM][PF 6 ], [BdMIM][BF 4 ]). In order to have information about reagent–ionic liquid interactions, the reaction was carried out over the temperature range (293.1–313.1 K). To study the effect of the amine on the rate and occurrence of the elimination reaction, several primary, secondary and tertiary amines with different structure (cyclic and acyclic), basicity and steric requirements were used. The data collected show that the reac…

Direct chemical grafted curcumin on halloysite nanotubes as dual-responsive prodrug for pharmacological applications

Covalently functionalized halloysite nanotubes (HNTs) were successfully employed as dual-responsive nanocarriers for curcumin (Cur). Particularly, we synthesized HNT-Cur prodrug with a controlled curcumin release on dependence of both intracellular glutathione (GSH) and pH conditions. In order to obtain HNT-Cur produgs, halloysite was firstly functionalized with cysteamine through disulphide linkage. Afterwards, curcumin molecules were chemically conjugated to the amino end groups of halloysite via Schiff's base formation. The successful functionalization of halloysite was proved by thermogravimetric analysis, FT-IR spectroscopy, dynamic light scattering and scanning electron microscopy. Ex…

A quantitative study of substituent effects on oxidative cyclization of some 2-aryl-substituted aldehyde thiosemicarbazones induced by ferric chloride and cupric perchlorate

As a development of our previous work, we performed a kinetic study of the oxidative cyclization reaction of some 2,4-diaryl-substituted aldehyde thiosemicarbazones 1a-n induced by ferric chloride and by cupric perchlorate. The results of cyclization of 1a-n were compared to those of the corresponding 2-methyl derivatives. The kinetic data were analyzed by means of the Hammett's equation.

Reazioni di isomerizzazione e trasposizione di fenilidrazoni in liquidi ionici: catalisi da sali di rame (II)

Stereoselective synthesis: from organoselenium to organocatalysis

Studies on the Stereoselective Selenolactonization, Hydroxy and Methoxy Selenenylation of α- and β-Hydroxy Acids and Esters. Synthesis of δ- and γ-Lactones.

Abstract The diastereoselective synthesis of hydroxy substituted γ- and δ-lactones was accomplished following two approaches. A 5- or 6-endo cyclization promoted by electrophilic selenium reagents of α- or β-hydroxy acids and a 5- or 6-exo cyclization of hydroxy esters obtained through a diastereoselective hydroxy selenenylation reaction of α- or β-hydroxy esters. Moreover, the diastereoselective methoxy selenenylation of the above compounds was investigated showing a case in which the compound that was unreactive in the hydroxy selenenylation conditions gave, in the methoxy selenenylation conditions, the deprotected diol. The usefulness of the methoxy selenenylation procedure was proven by…

Room temperature ionic liquids structure and its effect on the mononuclear rearrangement of heterocycles: an approach using thermodynamic parameters.

The kinetics of the rearrangement of the Z-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole (1) into the relevant 4-benzoylamino-2,5-diphenyl-1,2,3-triazole (2) induced by amines have been studied in five room-temperature ionic liquids (RTILs) at different temperatures. The kinetic data collected show that both cationic and anionic parts of RTILs significantly influence the reactivity of the title reaction. The calculated activation parameters allow us to advance hypotheses about the weak interactions operating in RTIL solutions.

Ionic Liquids binary mixtures: the influence of the composition on their properties and catalytic ability

Diimidazolium organic salts and supramolecular gels exerting antimicrobial activity

ChemInform Abstract: Methylation of 2-Phenylamino-1,3,4-thiadiazole. A Structure Debated.

The true identity of the 4-methyl-5-phenylimino-δ2-1,3,4-thiadiazoline (A) has been demonstrated. The reactions, previously reported in the literature to give A have been repeated and the structure of the compounds obtained has been established.

Synthesis and characterization of new polyamino-cyclodextrin materials.

With the aim of the synthesis of chemically modified cyclodextrins bearing polyamine pendant groups, potentially useful as capping agents for the preparation of nanosized metal systems or as auxiliaries for gene transfection, the reaction between the heptakis-(6-iodo)-(6-deoxy)-b-cyclodextrin and various polyamines has been explored. This synthetic approach allows obtaining materials constituted by mixtures of cyclodextrins, having different degrees of substitution, which were satisfactorily characterized by means of various complementary techniques (ESI-MS, NMR, potentiometric titration). The products obtained were successfully subjected to preliminary tests for their binding abilities tow…

Proline- and prolinamide-supported polystyrene: powerful and highly recyclable organocatalysts for the asymmetric aldol reaction

Supported proline and proline-derivatives as recyclable organocatalysts

In the last eight years, L-proline and L-proline derivatives, such as substituted prolinamides or pyrrolidines, have been successfully used as organocatalysts in several reactions. In this critical review we summarize the immobilization procedures of such organocatalysts highlighting their application, recoverability and reusability (86 references).

Reazione di eliminazione di Kemp: una sonda per lo studio delle proprietà microscopiche di liquidi ionici

Studio cinetico della reazione di eliminazione di 1,1,1-tribromo-2,2-bis(dimetossifenil)etano in liquidi ionici.

The importance of supramolecular reaction media in catalysis

New “AIE” Luminogens based on π-conjugated imidazolium salts

Simple and low loading catalysts for asymmetric aldol reaction under aqueous condition

ChemInform Abstract: Supported Proline and Proline-Derivatives as Recyclable Organocatalysts

In the last eight years, L-proline and L-proline derivatives, such as substituted prolinamides or pyrrolidines, have been successfully used as organocatalysts in several reactions. In this critical review we summarize the immobilization procedures of such organocatalysts highlighting their application, recoverability and reusability (86 references).

The effect of some amines and alcohols on the organized structure of [bmim][BF4] investigated by 1H NMR spectroscopy

The effect exerted by some amines and alcohols on the 1H NMR spectra of 1-butyl-3- methylimidazolium tetrafluoroborate [bmim][BF4] has been studied. This ionic liquid, which is one of the most widely used, is characterized by a high structural order degree, as a consequence of the symmetry and the coordination ability of the anion. In order to have information about the dependence of the detected effects on the alcohol or amine structure, some different primary, secondary and tertiary amines and alcohols have been considered. Furthermore, in the case of amines, their basicity has been also taken into account. Both amines and alcohols induce variation in chemical shifts values and signal mul…

Protonation equilibria of some ortho-substituted and annelated aryl and thiophen-2-yl and -3-yl ketones

For some phenyl- (1–8) and thiophen-2-yl (9–11) and thiophen-3-yl (12–14) ketones quantum-mechanical (PM3) calculations have been performed, and for compounds 2, 3, 5–8, 10–14 protonation equilibria have been determined. Phenyl ketones have similar values for the m* parameter and show good linear correlation between the proton affinities calculated in the gas phase and the measured pKBH+ values, which in turn parallel the trend for the calculated carbonyl–phenyl ring dihedral angle. It appears that the differences in basicity are governed essentially by “internal” factors (carbonyl–ring conjugation), while the base–conjugate acid differential solvation is not significantly affected by struc…

Supported Organocatalysts as a Powerful Tool in Asymmetric Synthesis

Organizzazione strutturale di liquidi ionici mono- e dicationici: un approccio combinato

Regioselective Epoxide Ring Opening. Steroselective Synthesis of a Tetrahydropyran Ring

The stereoselective synthesis of a 2-substituted tetrahydropyran with adjacent alkoxy-bearing stereogenic centre is described. The key steps of this synthesis were the stereoselective epoxidation of an allylic alcohol and the regioselective epoxide ring opening by lithium aluminum hydride. The regio and stereoselective synthesis of a trihydroxyselenide and a trihydroxysulfide is also described. The latter compounds are not suitable for cyclization to tetrahydrofuran ring.

Chemical and pharmaceutical evaluation of the relationship between triazole linkers and pore size on cyclodextrin–calixarene nanosponges used as carriers for natural drugs

Mixed cyclodextrin–calixarene nanosponges were used to prepare some composites with the well known polyphenolic bioactive compounds quercetin and silibinin. The composites were characterized by means of different techniques (UV-vis, FT-IR, microcalorimetry, thermogravimetry), in order to assess their loading and thermal stability. The kinetics of release of the bioactive molecules into aqueous solution were studied at two different pH values (1.0, 6.4), which mimic typical physiological conditions. Finally the possible antiproliferative effects in vitro were assayed towards three triple negative breast cancer cell lines (SUM 149, SUM 159 and MDA-MB-23). Our results point out the role assume…

Diimidazolium-based organic salts as low molecular weight hydro- and organogelator

"Sweet" Ionic Liquids Gels: Properties and Applications

Oxidative cyclization of some aldehyde semicarbazones induced by metallic salts

The oxidative cyclization of some aldehyde semicarbazones 10 with four different oxidizing agents has been effected. The structure of the semicarbazones and the nature of cyclizing agent affected the rate and yield of cyclization but they did not show any influence on the regiochemistry of reaction. In fact, 1,2,4-triazoline 20 was the only heterocyclic ring obtained by the cyclization reaction.

New recyclable catalysts for direct asymmetric aldol reaction. L-proline or H-Pro-Pro-Asp-NH2 immobilized on new ionic liquid modified silica gels

“Nonsolvent” Applications of Ionic Liquids in Organocatalysis

This chapter is organized in three sections (see Figure 10.1 ): 2. Immobilization of ionic liquids and organocatalysts 2.1 Covalently attached “ ionic liquid ” moieties as supports 2.2 Covalently attached “ ionic liquid ” moieties as linkers 2.3 Covalently attached “ ionic liquid ” moieties as organocatalysts

STABILITY OF ELECTROGENERATED N-HETEROCYCLIC CARBENES FROM IONIC LIQUIDS. THE BOUNDARY CONDITIONS

Water in stereoselective organocatalytic reactions

In this review, recent advances in asymmetric organocatalytic reactions carried out with variable amounts of water, from substoichiometric to a large excess (reaction medium), are discussed. We also summarize several proposed mechanisms for the different possibilities of the action of water both in the increased activity of the catalyst and in the asymmetric induction. Finally, the application of this catalytic methodology to the enantioselective synthesis of valuable compounds through enamine or iminium catalysis is presented.

Task-specific dicationic ionic liquids used as reaction media for Michael addition

The “perturbative” effect of cosolvents on the structure of neat bmimBF4 and bmimNTf2 evaluated by means of kinetic measurements.

Cyclodextrin-[60]fullerene conjugates: synthesis, characterization, and electrochemical behavior

Three different functionalized β-cyclodextrins (β-CDs) bearing the C60 moiety linked covalently have been prepared in good yields by reaction between the parent β-CD and [60]fullerene via 1,3-dipolar cycloaddition. These compounds have been fully spectroscopically characterized and their electrochemical behavior has been investigated. Surprisingly, the electrochemical properties of the C60 cage remain unaltered even after chemical functionalization, making these systems very appealing as supramolecular hosts for electron-transfer processes.

Reactivity of phenylhydrazones in ionic liquids solution: the effect of copper(II) salts

π-Conjugated diimidazolium salts: rigid structure to obtain organized materials.

Phenylene ethynylene based diimidazolium salts differing in the alkyl chain length borne on the imidazolium ion and anion nature were synthesized. Their properties were studied both in solution and in the solid state. Salts obtained were able to aggregate in organic solvent solution. Aggregate formation was studied by performing concentration dependent measurements using UV-vis, fluorescence and Resonance Light Scattering. Furthermore, features of the aggregates were also investigated in the solid state by means of fluorescence and Scanning Electron Microscopy measurements. Finally, Density Functional Theory calculations were performed to obtain insights into the interaction geometry in the…

Binary Mixtures of Ionic Liquids: A Joint Approach to Investigate their Properties and Catalytic Ability

The growing interest in the properties and applications of ionic liquids has recently led to research into the possibility of using their binary mixtures. This work reports on the effects of binary mixtures of ionic liquids on the outcome of organic reactions such as the mononuclear rearrangement of heterocycles and the solvatochromic behavior of Nile Red. Binary mixtures formed by ionic liquids differing in the structure of the cation and the anion are taken into account. In particular, ionic liquids such as 1-benzyl-3- butylimidazolium bis(trifluoromethanesulfonyl)imide, 1-(2,3,4,5,6- pentafluorobenzyl)-3-butylimidazolium bis(trifluoromethanesulfonyl)imide, and 1-benzyl-3-butylimidazolium…

1,2,3-Oligotriazoles modified halloysite nanotubes as potential active biological species: synthesis and characterization

In the last years, the development of nano-formulations for cancer treatment represents one of the major challenges of the scientific research. The prodrug strategy, that combines chemotherapeutic agents with nanocarriers such as halloysite nanotubes (HNTs), is a promising strategy both to improve the biological activity of the drug molecules and to reduce the side effects of drugs. Herein we report the synthesis and characterization of a HNTs prodrug based on 1,2,3-triazole units covalently linked to HNTs external surface, bearing different positively charged moieties, which could present interesting pharmacological activities.

A joint experimental and computational study on the oxidative cyclization of aldehyde thiosemicarbazones induced by potassium ferricyanide and by tris(p-bromophenyl)amino hexachloroantimoniate.

Studio cinetico della reazione di sostituzione nucleofila aromatica di alcuni 2-X-3-nitro e 2-X-5-nitrotiofeni in BMIMBF4.

IONOGEL IBRIDI: SISTEMI ADSORBENTI PER LA RIMOZIONE DI COMPOSTI FARMACEUTICI DALLE ACQUE INQUINATE

New recyclable materials for L-proline-catalyzed aldol reactions

SYNTHESIS AND EVALUATION OF CATALYTIC ACTIVITY IN WATER AND MICROWAVE IRRADIATION OF A NEW SUPPORT BASED ON HNT TRIAZOLIUM SALTS

In the last years SILLP (supported ionic liquid-like phase)-based materials prepared by covalent attachment have been synthesized [1]. Recently, we have synthesized a palladium-based catalytic system using halloysite nanotubes modified with octylimidazolium moieties and we have tested it in the Suzuki cross-coupling reaction under traditional heating, microwave irradiation and a very small amount of Pd catalyst [2,3]. It is known that support based on triazole motif showed superior activity to the analogous imidazole molecules [4] so, we have focused our attention to develop a new SILLP system with triazolium moiety. Herein we report the synthesis of an original Pd-dicationic triazolium sup…

Stereocontrolled approach to δ- and γ-lactones and 1,3-diols. The role of X− ion in the selenolactonization

Abstract Two complementary approaches have been realized for the stereoselective synthesis of 4,6-disubstituted δ-lactones and 1,3- anti and syn diols. In the 6- endo selenolactonization the role of the X − ion on the stereoselectivity is shown. Moreover, the highly stereoselective transformation of the 6- endo δ-lactone to the 5- exo γ-lactone is reported.

A spectrofluorimetric study of binary fluorophore-cyclodextrin complexes used as chiral selectors

Abstract Six binary complexes between three fluorophores (pyrene, xanthone and anthraquinone) and β-cyclodextrin (β-CD) or heptakis-(6-amino)-(6-deoxy)-β-cyclodextrin (am-β-CD) were tested at two pH values (8.0 and 9.0) as chiral selectors for three α-amino acids chosen as model. The conditional constant (β2T) values for ternary complexes (fluorophore-CD-amino acid), determined by means of fluorescence spectroscopy, showed that the binary complexes are suitable receptors for chiral recognition. The effect of α-amino acids on stability and stoichiometric ratio of the binary complexes has also been studied. The binary complexes were in most cases stabilized by adding the ternary agent. The tr…

Spectrophotometric study on the thermodynamics of binding of α- and β-cyclodextrin towards some p-nitrobenzene derivatives

Binding properties of native alpha- and beta-cyclodextrin towards some nitrobenzene derivatives have been studied by means of UV-vis spectrophotometry. The former host is able to form complexes having 1 : 1 and 1 : 2 stoichiometric ratios with these guests, while only 1 : 1 complexes are detected with the latter host. A careful analysis of the thermodynamic parameters for complexation equilibria, under the perspective of the enthalpy-entropy compensation effect, reveals that binding abilities of the two different hosts are subject to different features.

ChemInform Abstract: Di- and Tricationic Organic Salts: An Overview of Their Properties and Applications

During recent years growing interest has been devoted to the synthesis and applications of polycationic organic salts. Among them, di- and tricationic organic salts can be considered the natural evolution of monocationic ones. These last have given rise to the large class of ionic liquids. In the cases of di- and tricationic organic salts, the potential to change their structural features simply by varying the properties either of the charged heads or of the spacers separating them provides the opportunity to obtain materials suitable for different applications. This review article highlights recent progress in the study of the properties of di- and tricationic organic salts, as well as in …

Polarimetry as a useful tool for the determination of binding constants between cyclodextrins and organic guest molecules

Binding constants for cyclodextrin inclusion complexes can be easily estimated by means of simple polarimetric measurements. Determinations are as reliable and accurate as those obtained by means of other more sophisticated techniques, and take advantage by the limited waste of material required. Our results are briefly compared with literature values obtained by means of different techniques.

Complexation equilibria between beta-cyclodextrin and p-nitroaniline derivatives in mixed solvent media: a polarimetric study

ChemInform Abstract: Stereocontrolled Approach to δ- and γ-Lactones and 1,3-Diols. The Role of X- Ion in the Selenolactonization.

Abstract Two complementary approaches have been realized for the stereoselective synthesis of 4,6-disubstituted δ-lactones and 1,3- anti and syn diols. In the 6- endo selenolactonization the role of the X − ion on the stereoselectivity is shown. Moreover, the highly stereoselective transformation of the 6- endo δ-lactone to the 5- exo γ-lactone is reported.

ChemInform Abstract: Sequential Suzuki/Asymmetric Aldol and Suzuki/Knoevenagel Reactions under Aqueous Conditions.

Here we describe for the first time a sequential Suzuki/asymmetric aldol reaction. Such sequential approach was achieved through the combined use of an ionic liquid supported palladium catalyst and the organocatalyst trans-4-(2,2-diphenylacetoxy)proline. Suzuki and asymmetric aldol reactions were performed under aqueous conditions. The use of a palladium catalyst under basic conditions allowed also the first example of sequential Suzuki/Knoevenagel reaction. Reactions were carried out under aqueous conditions and products were isolated in good to high yields and, in the case of the Suzuki/aldol reaction, with diastereoselectivities up to 91:9 and enantioselectivities up to at least 99 %.

Sali di dialchilimidazolio: dai liquidi ionici agli organogel

Polystyrene-supported organocatalysts for alfa-selenenylation and Michael reactions. A common post-modification approach for catalytic differentiation

Three different resin-supported catalysts have been prepared by using the well established post-modification approach by means of thiol-ene coupling reaction. Two catalysts were tested for the first time in the asymmetric α-selenenylation of propanal, while the third catalyst was used in the Michael addition reaction. While the preliminary results are not encouraging in the case of supported Jørgensen’ catalyst, interesting data have been collected with both for the supported MacMillan and prolyl-prolinol catalysts. In fact, these catalysts displayed good activity and selectivity. A reversed enantioselectivity in the α-selenenylation was observed by changing the polarity of the solvent. Fin…

Photoluminescent hybrid nanomaterials from modified halloysite nanotubes

The synthesis of photoluminescent nanomaterials based on halloysite nanotubes is described. The obtained hybrid was characterized by means of TGA, FT-IR, DLS and XPS measurements; in addition its morphology was imaged by TEM and HR-TEM. The HNT hybrid also exhibited photoluminescent properties, both in solution and in the solid state, and white-light emission (0.24, 0.36; CIE coordinates) was observed. This work could be pioneering as a new strategy for manufacturing both LEDs and fluorescent tags based on HNT nanomaterials. © 2018 The Royal Society of Chemistry.

A joint of experimental investigations about the structural organization of two geminal ionic liquids

Geminal Ionic Liquids: A Combined Approach to Investigate their Tridimensional Structure

Different investigations, such as 1D and 2D NMR spectroscopy, resonance light scattering spectroscopy and molecular dynamics simulations, have been jointly used to achieve a deeper understanding of the degree of structural order in two geminal ionic liquids. In particular, 3,3’-di-n-butyl-1,1’-(1,3- phenylenedimethylene)diimidazolium and 3,3’-di-n-butyl-1,1’-(1,4-phenylenedimethylene) diimidazolium bis- ACHTUNGTRENUNG[bis(trifluoromethanesulfonyl)imide] have been studied. These geminal ionic liquids were chosen because of the presence of both a rigid phenylenedimethylene link between two imidazolium rings, which should give a high degree of order to the solvent system, and the different sha…

Ionogels formed by geminal imidazolium salts: a preliminary investigation

GLYCOCLUSTER A BASE DI NANOTUBI DI ALLOSITE COME DRUG DELIVERY SYSTEM

Le interazioni carboidrati–lectine giocano un ruolo fondamentale in diversi processi biologici come ad esempio nelle infiammazioni, embriogenesi, sviluppo cellulare, etc..1 Sebbene l’interazione tra lectine e carboidrati sia un’interazione debole, la possibilità di instaurare contemporaneamente interazioni multiple tra differenti unità di lectine e differenti unità di carboidrati ne aumenta l’efficienza e la selettività.2 Nella presente comunicazione si riporta la sintesi di nuovi glicocluster basati su nanotubi di allosite, a cui sono state chimicamente legate unità ciclodestriniche che presentano sul bordo largo unità zuccherine quali galattosio, mannosio e lattosio. I materiali ottenuti …

Supported Organocatalysts as a Powerful Tool in Organic Synthesis

no abstract

Geminal Ionic Liquids: an electrochemical approach to investigate their reactivity and stability vs. traditional monocationic ionic liquids

Polarimetry as a useful tool for the study of binding equilibria between cyclodextrins and some suitably sized and structured organic molecules

Nitrogen-Doped Carbon Nanodots-Ionogels: Preparation, Characterization, and Radical Scavenging Activity

Hybrid diimidazolium-based ionogels were obtained by dispersing nitrogen-doped carbon nanodots (NCNDs) in ionic liquid (IL) solutions and by using dicationic organic salts as gelators. The properties of the NCND-ionogels were studied in terms of thermal stability, mechanical strength, morphology, rheological, and microscopic analyses. Insights into the formation of the hybrid soft material were attained from kinetics of sol-gel phase transition and from estimating the size of the aggregates, obtained from opacity and resonance light-scattering measurements. We demonstrate that, on one hand, NCNDs were able to favor the gel formation both in the presence of gelating and nongelating ILs. On t…

Immobilizzazione di dipeptidi su resina polistirenica ed impiego in sintesi stereoselettive: risultati preliminari

Effect of linear 5-alkyl substituents on the rearrangement rate of the Z-phenylhydrazones of some 5-alkyl-3-benzoyl-1,2,4-oxadiazoles

Nanocomposite based on Multi-Macrocyclic Receptors and Halloysite for Volatile Organic Compounds Capture

Volatile organic compounds (VOCs) are chemicals released to the atmosphere by natural and anthropogenic sources. VOCs are hazardous air pollutants and promote formation of photochemical smog. Variety of chemicals released from pharmaceutical industry includes priority pollutants like benzene, toluene, and dichloromethane. The aim of this work was at designing, preparing and characterizing from the physico-chemical view-point a pseudo nano-sponge with low environmental impact for pollutant removal. As adsorbent material, a nanocomposite based on nanoclay and cucurbiturils, which are biocompatible materials, were investigated. Clay minerals (e.g. montmorillonite and kaolin) are important comp…

Z-Phenylhydrazones of 3-benzoyl-1,2,-oxadiazole: investigation of behaviour in solution and in the gas phase.

Studio spettrofotometrico della formazione di coppie ioniche ammina/p-nitrofenolo in liquido ionico

SYNTHESIS AND CHARACTERIZATION OF POSITIVELY CHARGED FUNCTIONALIZED HALLOYSITE/CURCUMIN SYSTEMS AND EVALUATION OF THEIR ANTICANCER ACTIVITY

Phenolic compound originated from one of the main class of secondary metabolites, as curcumin and its derivatives have been studied and their biological and pharmacological activities have been evaluated, too [1,2]. Unfortunately, curcumin exhibits poor bioavailability after oral or topic administration [3]. Therefore a carefully designed carrier could significantly facilitate curcumin delivery and broaden the range of its possible pharmaceutical applications. Halloysite was found to be a viable and inexpensive nanoscale container for the encapsulation of biological active molecules [4]. In this communication we report data about a new potential curcumin carrier based on positively charged …

Multi-layered, covalently supported ionic liquid phase (mlc-SILP) as highly cross-linked support for recyclable palladium catalysts for the suzuki reaction in aqueous medium

The reaction between an excess of 1,4-bis(3-vinylimidazolium-1-yl) bromide and a mercaptopropyl-modified amorphous silica gel or ordered mesoporous silica SBA-15 in the presence of azobisisobutyronitrile (AIBN) afforded new materials, which have a high loading of imidazolium moieties. These materials, which contain a highly cross-linked polymeric network, have been denoted as multi-layered, covalently supported ionic liquid phase (mlc-SILP) and have been used as support for palladium catalysts containing a high loading of the metal (10 wt%). Such materials were characterized by several techniques (13C magic angle spinning nuclear magnetic resonance, the Brunauer–Emmett–Teller technique, sma…

A study of synergetic effect of ionic liquids and ultrasounds on the aryl azides formation

Organocatalizzatori e liquidi ionici supportati: nuovi materiali in sintesi organica

Nell’ultimo decennio l’organocatalisi e i liquidi ionici hanno rappresentato due campi di grande interesse scientifico. Gli organocatalizzatori hanno trovato particolare impiego in sintesi enantioselettive conducendo a prodotti finali con alte rese e selettività. I liquidi ionici sono stati estensivamente utilizzati come solventi alternativi e, opportunamente modificati, come catalizzatori o loro supporti. Uno sviluppo attuale che accomuna questi due campi di ricerca consiste nella possibilità di immobilizzazione di organocatalizzatori e liquidi ionici per trasformarli in materiali riciclabili con ampie capacità di utilizzo in chimica organica. Negli ultimi anni, il nostro gruppo di ricerca…

Photosynthesized silver-polyaminocyclodextrin nanocomposites as promising antibacterial agents with improved activity

Ag nanocomposites were prepared by photoreduction of ammoniacal silver acetate in the presence of poly-{6-[3-(2-(3-aminopropylamino)ethylamino)propylamino]}-(6-deoxy)-β-CD (amCD). The obtained systems were characterized by means of various complementary techniques (UV-vis, FT-IR, TEM, SAED). In particular, FT-IR spectroscopy evidenced a partial oxidative degradation of the polyamine branches of the capping auxiliary, due to the fact that these groups function as a sacrificial reducing agent in the photoinduced formation of the Ag metal core. TEM and SAED micrographs showed that the Ag cores possess a relatively low polydispersity and a significantly crystalline character. The Ag–amCD system…

Synthesis, characterization and study of covalently modified triazole LAPONITE® edges

Abstract LAPONITE® (Lap) clay mineral was successful functionalized by triazole groups in a two steps procedure. First, the Lap edges were modified with 3-azidopropyltrimethoxysilane by traditional heating and microwave irradiation. Microwave irradiation allowed us to obtain high loading onto the Lap edges in lower times compared to those obtained through conventional method. Afterwards, the triazole moieties were obtained by reaction between azido functionalized Lap and propargyl alcohol. The successful functionalization of Lap was proved by thermogravimetric analysis, FT-IR spectroscopy, dynamic light scattering and ζ-potential measurements. Finally, the effects of the surface modificatio…

Asymmetric aldol reaction in water catalyzed by polystyrene-supported proline

Influenza dei liquidi ionici sulla reazione di trasposizione eterociclica mononucleare catalizzata da Cu(II)

ChemInform Abstract: Sol-Gel Entrapped Chromium(VI): A New Selective, Efficient and Recyclable Oxidizing System.

Abstract The sol-gel entrapment of chromium(VI) within a silica matrix, obtained by oxidation with ozone of the corresponding entrapped chromium(III), was found to be an efficient and recyclable oxidizing system (at least up to 16 times) for benzylic alcohols. No leaching of chromium in solution was observed, which prevented any environmental pollution.

Stability and stoichiometry of some binary fluorophore-cyclodextrin complexes

The stability and stoichiometric ratio of binary complexes among five fluorophores and β-cyclodextrin (β-CD) or heptakis-(6-amino-6-deoxy)-β-cyclodextrin (am-β-CD) were determined by means of fluorescence measurements in borate buffer at pH=8.0 and 9.0. Structure of both host and guest affected the characteristics of the binary complexes. Pyrene and anthraquinone formed a 1:2 (fluorophore: cyclodextrin) complex with both cyclodextrins. Xanthone formed 1:1 complex with β-CD and 1:2 complex with am-β-CD. A more defined behaviour was observed for crysene. In fact, both stoichiometric different complexes were detected with both hosts. Only 1:1 complexes were observed for antracene. The complex …

Catalytic properties of Ag-PolyaminoβCD NPs for reduction of nitroarenes

The reduction of nitroarenes is a key reaction involved in the synthesis of several compounds such as drugs, pesticides or dyes. During the last years Pd and Ag NPs have been used as catalysts to carry out this reaction with NaBH4. However several mechanistic aspects of the process are still unclear; in particular there is not agreement about the kinetic order of these reactions, whether 0-th or 1-st order in the substrate[1]. The aim of this work is to use a novel catalytic systems constituted by Ag-NPs coated with different polyamino-βCDs (Figure 1)[2], to carry out the reduction of some aromatic nitrocompounds using NaBH4 as the reducing agent, and to determine the kinetic features of th…

Organogel formed by imidazolium salts: molecular recognition processes

ChemInform Abstract: Gas-Phase and Solution Basicities of Some Alkyl 2,6-Dialkylphenyl Ketones: A Comparative Analysis.

Abstract The gas-phase basicity of a number of alkyl 2,6-dialkylphenyl ketones (2,6-R2C6H3COR′) has been found to be almost insensitive to structural variations, as a result of a compensation of steric and electronic effects associated with the bulkiness and to the polarizability, respectively, of R and/or R′. On the contrary, the basicity in concentrated sulfuric acid undergoes, along the same series of compounds, a variation of nearly 8 pK units, as a consequence of steric inhibition of solvation of the protonated carbonyl as the main effect played by R and/or R′. The results in the condensed phase agree very nicely with recent findings relevant to some 4-substituted 2,6-dimethylacetophen…

ChemInform Abstract: First Evidence of Proline Acting as a Bifunctional Catalyst in the Baylis-Hillman Reaction Between Alkyl Vinyl Ketones and Aryl Aldehydes.

Proline in the presence of sodium hydrogen carbonate has been found to be an effective catalyst for the Baylis–Hillman reaction between methyl or ethyl vinyl ketone and aryl aldehydes. Screening of several amine catalysts showed that an ionizable carboxylic function directly linked to the secondary amine catalyst plays an important role in the synthesis of the desired product in good yield. The data obtained has allowed us to suggest, for the first time, that proline, sarcosine, pipecolinic acid and homoproline may act as bifunctional catalysts via a bicyclic enaminolactone species as intermediate. Quantum-mechanical calculations (PM3/COSMO and ab initio 3-21G/COSMO) support this mechanism …

Organic salts and aromatic substrates in two-component gel phase formation: the study of properties and release processes

To identify gel phases able to act as confined reaction media or materials for the removal of organic pollutants, we studied two-component gel phases formed by naphthalenedisulfonate diimidazolium salts in the presence of some organic guests, in 1-propanol solution. Guests differing in π-surface area, bulkiness and electronic properties were taken into account. Soft materials obtained were investigated for their thermal stability, self-repairing ability and morphology. Furthermore, two-component gel phase formation was studied using resonance light scattering (RLS) measurements. Guest release processes from the gel phase were also studied. These processes were monitored as a function of tim…

A study of the influence of ionic liquids properties on the Kemp elimination reaction

The morpholino-induced elimination of 5-nitrobenzisoxazole into the relevant 2-cyano-4-nitrophenolate has been used as a sample reaction in order to investigate molecular properties of some room temperature ionic liquids. The kinetic study was carried out at 298 K by means of spectrophotometric measurements. Ionic liquids, which differ in both their cation and anion properties, were used as solvent systems. In particular, aliphatic (pyrrolidinium, piperidinium, and ammonium) and aromatic (imidazolium and pyridinium) ionic liquids were used. For aromatic cations, imidazolium ions having different hydrogen-bond donor ability or a different alkyl-chain length were taken into account. The anion…

Diastereoselective Synthesis of 2-Phenylselenenyl-1,3-anti-Diols and 2-Phenylselenenyl-1,3-anti-Azido-Alcohols via Hydroxy- and Azido-Selenenylation Reactions

A method to synthesize 2-phenylselenenyl-1,3-anti-diols and 2-phenyl- selenenyl-1,3-anti-azidoalcohols via hydroxy- or azido-selenenylation of trans-allylic alcohols is reported. Moreover, the first example of hydroxyl-selenenylation of an allylic azide is presented. Yields ranging from moderate to good and diastereomeric ratios up to 95:5 are achieved.

ChemInform Abstract: Water in Stereoselective Organocatalytic Reactions

In this review, recent advances in asymmetric organocatalytic reactions carried out with variable amounts of water, from substoichiometric to a large excess (reaction medium), are discussed. We also summarize several proposed mechanisms for the different possibilities of the action of water both in the increased activity of the catalyst and in the asymmetric induction. Finally, the application of this catalytic methodology to the enantioselective synthesis of valuable compounds through enamine or iminium catalysis is presented.

Oxidative degradation properties of Co-based catalysts in the presence of ozone

Four series of cobalt-based catalysts, such as bare Co3O4 and CoO, CoOx-CeO2 mixed oxides, CoOx supported over alumina and alumina-baria and CoMgAl and CoNiAl hydrotalcites have been synthesized and investigated for the oxidative degradation of phenol in the presence of ozone. Characterizations were obtained by several techniques in order to investigate the nature of cobalt species and their morphological properties, depending on the system. Analyses by XRD, BET, TPR, UV-visible diffuse reflectance spectroscopy and TG/DT were performed. The CoNiAl hydrotalcite exhibits, after 4 h of reaction, the highest phenol ozonation activity followed by Co(3 wt%)/Al2O3-BaO and CoMgAl. The samples Co(1 …

Non-stoichiometric dicationic organic salts form supramolecular gels

Studio delle proprietà di ionogel formati da sali organici dicationici

Mononuclear rearrangement of heterocycles in zwitterionic micelles of amine oxide surfactants.

Abstract Rate constants for the mononuclear rearrangement (MRH) of Z -phenylhydrazones of some 5-substituted-3-benzoyl-1,2,4-oxadiazoles in water have been measured in the presence of zwitterionic micelles. The use of micellized N -tetradecyl- N , N -dimethylamineoxide (C 14 DMAO) as the reaction medium allowed to solubilize the otherwise water-insoluble oxadiazoles. Micellar rate effects were analyzed by using a simple pseudo-phase model and compared with those obtained in non-ionic micelles (Triton X-100). Evidence that both the rate of the rearrangement reaction and the binding of the substrates to the micelles are mainly governed by substrate hydrophobicity is obtained. The disagreement…

Sali di imidazolio multistrato supportati covalentemente: attività catalitica per la produzione di carbonati ciclici in scCO2 e nuovi supporti per catalizzatori di palladio

I liquidi ionici supportati (SILP) hanno trovato interessanti applicazioni sia nel campo delle reazioni catalizzate da metalli che in organocatalisi [1]. Inoltre, i SILP sono stati efficacemente impiegati in reazioni di apertura di epossidi in CO2 supercritica per fornire carbonati ciclici [2]. I liquidi ionici vengono generalmente supportati covalentemente attraverso la modificazione dei gruppi funzionali presenti sulla superficie del supporto, conducendo in tal modo alla formazione di un monostrato di liquido ionico supportato. Gli esempi di SILP legati covalentemente, in maniera tale da ottenere dei multistrato, sono rari. In questa comunicazione viene riportato un metodo per preparare d…

ChemInform Abstract: Stereoselective Synthesis of Substituted Tetrahydropyran Rings via 6-exo and 6-endo Selenoetherification.

Eight unsaturated alcohols were cyclized by selenoetherification in 6-exo or 6-endo manner to give substituted tetrahydropyran rings. Yields, regio- and stereoselectivities were discussed in terms of steric and electroniceffects such as Se-O interaction. For the first time examples of the use of silica gel in selenoetherification and the effect of the X - counter ion of PhSe + on the reaction course are discussed. These effects are related to the occurrence of Se-O interaction.

On the characterization of some [bmim][X]/co-solvent binary mixtures: a multidisciplinary approach by using kinetic, spectrophotometric and conductometric investigations

Abstract In order to study the intrinsic characteristics and to evaluate the structural variations determined by the addition of a co-solvent to 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF 4 ]) we examined the behaviour of some probes in [bmim][BF 4 ]/co-solvent binary mixtures. The rate constants of the piperidino-catalyzed rearrangement of the Z -phenylhydrazone of the 3-benzoyl-5-phenyl-1,2,4-oxadiazole into the relevant 4-benzoylamino-2,5-diphenyl-1,2,3-triazole as well as the spectrometric properties of pyrene and Nile Red were evaluated. With the same purpose also 1 H NMR and conductivity measurements were carried out. By comparison the behaviour of 1-butyl-3-methylimidaz…

Ionic liquids binary mixtures and zeolites: a combination to promote carbohydrates conversion into 5-hydroxymethylfurfural

The Gelling Ability of Some Diimidazolium Salts: Effect of Isomeric Substitution of the Cation and Anion

The gelling ability of some geminal imidazolium salts was investigated both in organic solvents and in water solution. Organic salts differing either in the cation or anion structure were taken into account. In particular, the effects on the gel-phase formation of isomeric substitution on the cation or anion as well as of the use of mono- or dianions were evaluated. As far as the cation structure is concerned, isomeric cations, such as 3,3′-di-n-octyl-1,1′-(1,4-phenylenedimethylene)diimidazolium and 3,3′-di-n-octyl-1,1′-(1,3-phenylenedimethylene)diimidazolium, were used. On the other hand, in addition to the bromide anion, isomeric dianions, such as the 1,5- and 2,6-naphthalenedisulfonate a…

Sintesi efficiente mediata da microonde di derivati di fullerene per dispositivi fotovoltaici organici

ChemInform Abstract: Eco-Friendly Functionalization of Natural Halloysite Clay Nanotube with Ionic Liquids by Microwave Irradiation for Suzuki Coupling Reaction.

Abstract Microwave assisted halloysite (HNT) external surface functionalization with ionic liquids is described. HNTs modification was achieved in two steps: a) grafting of 3-mercaptopropyl trimethoxysilane on the external surface of HNT by a microwave irradiation; b) anchorage of vinylimidazolium ionic liquids by a thiol-ene reaction. MW irradiation allowed us to obtain high loading onto the HNT surface compared to those obtained through conventional synthesis. Fourier transform infrared spectroscopy and thermogravimetric analysis confirmed that the grafting has occurred only on the external surface of HNT. Turbidimetric and dynamic light scattering analyses showed that the introduction of…

Ionic liquid binary mixtures: How different factors contribute to determine their effect on the reactivity

We studied how mixing ionic liquids affected the rate of the Diels Alder reaction between 9-anthracenemethanol and N-ethylmaleimide. The mixtures considered spanned the whole compositional range and differed for the anion or the cation. These comprised mixtures of the ionic liquid 1-benzyl-3-butyl-imidazolium bis-(trifluoromethanesulfonyl)imide ([Bzbim][NTf2]) with 1-(2,3,4,5,6-pentafluorophenyl)-3-butyl-imidazolium bis-(trifluoromethanesulfonyl)imide ([Bz(F5)bim][NTf2]) or 1-benzyl-3-butyl-imidazolium tetrafluoroborate ([Bzbim][BF4]). Moreover we studied the reaction in a set of mixtures containing an aliphatic and an aromatic cation, namely [Bzbim+] and N-butyltriethylammonium ([bEt3N+]) …

Evidences of the organising ability of ionic liquids on the rate of the elimination reaction.

ChemInform Abstract: Oxidative Cyclization of Some Aldehyde Semicarbazones Induced by Metallic Salts.

The oxidative cyclization of some aldehyde semicarbazones 10 with four different oxidizing agents has been effected. The structure of the semicarbazones and the nature of cyclizing agent affected the rate and yield of cyclization but they did not show any influence on the regiochemistry of reaction. In fact, 1,2,4-triazoline 20 was the only heterocyclic ring obtained by the cyclization reaction.

Aggregation processes of perylene bisimide diimidazolium salts

The supramolecular aggregation of three diimidazolium- functionalized perylene bisimides, differing in the alkyl chain length was investigated. These salts form aggregates in solvents like chloroform, dichloromethane, and glycerol. Solvent-, concentration-, and temperature-dependent spectroscopic studies were carried out, evidencing the occurrence of an isodesmic, enthalpy-driven aggregation process, underpinned by p–p stacking and hydrogen bonding. Moreover, dynamic light scattering (DLS) measurements and SEM images revealed that these salts aggregate in chloroform into elongated structures.

Supported ionic liquids. New recyclable materials for the L-proline-catalyzed aldol reaction

New materials for L-proline recycling have been developed. These materials have been applied to the L-proline-catalyzed aldol reaction between acetone and several aldehydes. The L-proline has been supported on the surface of modified silica gels with a monolayer of covalently attached ionic liquid with or without additional adsorbed ionic liquid. Good yields and ee values, comparable with those obtained under homogeneous conditions, have been obtained especially with imidazolinium-modified and 4-methylpyridinium-modified silica gels. Moreover, these materials have been easily recovered by simple filtration and studies about their reuse have been carried out. These studies showed that these …

A multivariate insight into ionic liquids toxicities

A multivariate insight into Ionic Liquids' (ILs) toxicity, a broad term highly dependent on the biological systems adopted as “sensors”, addressed four main groups of toxicities: aquatic toxicity, toxicity towards fungi and bacteria, cytotoxicity towards IPC-81 rat cell lines and acetylcholinesterase enzyme inhibition. This approach, summarizing toxicity information available from a huge amount of scattered literature data, allowed derivation of aquatic toxicity scores for 104 ILs and bacteria and fungi toxicity scores for 87 ILs as well as identification of a correlation between aquatic ecotoxicity and the response of IPC-81 rat cell lines. Further evidence on the effects of cation structu…

Solution and thermal behaviour of novel dicationic imidazolium ionic liquids

A new class of functionalised dicationic ionic liquids, containing a central cationic unit capped by a basic functionality (imidazole), has been synthesised. These salts have been characterised in isotropic solution using proton and 2D-NMR spectroscopy, and their thermal stability has been studied by DSC and TGA. All these novel salts contain the 1-(1-imidazolylmethyl)-3,5-di{1-(3'-octylimidazolylmethyl)}-benzene cation as a defining structural motif. Salts of both singly and doubly charged anions were prepared and, in particular, the selected monoanions (Br(-), [BF4](-), or [NTf2](-)) differ in size, shape and hydrogen-bonding ability, whereas the dianions differ in the nature of the space…

Geminal ionic liquids: a combined approach to investigate their three-dimensional organisation.

Different investigations, such as 1D and 2D NMR spectroscopy, resonance light scattering spectroscopy and molecular dynamics simulations, have been jointly used to achieve a deeper understanding of the degree of structural order in two geminal ionic liquids. In particular, 3,3'-di-n-butyl-1,1'-(1,3-phenylenedimethylene)diimidazolium and 3,3'-di-n-butyl-1,1'-(1,4-phenylenedimethylene)diimidazolium bis[bis(trifluoromethanesulfonyl)imide] have been studied. These geminal ionic liquids were chosen because of the presence of both a rigid phenylenedimethylene link between two imidazolium rings, which should give a high degree of order to the solvent system, and the different shapes of the two cat…

Self-Sustaining Supramolecular Ionic Liquid Gels for Dye Adsorption

Water contamination is one of the main problems of modern society, and scientific research is continuously involved in identifying solutions able to preserve this valuable source. In this context, we characterized novel ionogels formed by organic salts with different anions. In particular, they show self-strengthening behavior, a quite unusual property for supramolecular gels, and they also exhibit a good load-bearing capacity. These ionogels are able to remove cationic dyes from wastewater. Thanks to their properties, they can be used in different apparatuses like dialysis membranes and as loading in adsorption columns. In the latter case over 95% removal is achieved in less than 10 min. I…

Substituent effect on oxidative cyclization of aldehyde thiosemicarbazones with ferric chloride

The reactivity of aldehyde thiosemicarbazones 1 with ferric chloride solutions was examined. When compounds 1 are not substituted on the N-2 nitrogen atom formation of 1,3,4-thiadiazole 3 heterocyclic ring was observed. In contrast 1,2,4-triazoline 4 and/or 1,3,4-thiadiazoline 5 heterocyclic rings were afforded when N-2 nitrogen atom carried a methyl or a phenyl group. The reaction mechanism is also discussed.

Study of aromatic nucleophilic substitution with amines on nitrothiophenes in room-temperature ionic liquids: are the different effects on the behavior of para-like and ortho-like isomers on going from conventional solvents to room-temperature ionic liquids related to solvation effects?

The kinetics of the nucleophilic aromatic substitution of some 2-L-5-nitrothiophenes (para-like isomers) with three different amines (pyrrolidine, piperidine, and morpholine) were studied in three room-temperature ionic liquids ([bmim][BF4], [bmim][PF6], and [bm(2)im][BF4], where bmim = 1-butyl-3-methylimidazolium and bm(2)im = 1-butyl-2,3-dimethylimidazolium). To calculate thermodynamic parameters, a useful instrument to gain information concerning reagent-solvent interactions, the reaction was carried out over the temperature range 293-313 K. The reaction occurs faster in ionic liquids than in conventional solvents (methanol, benzene), a dependence of rate constants on amine concentration…

Halloysite nanotubes as support for metal-based catalysts

Halloysite nanotubes (HNTs) are clay minerals with a hollow nanotubular structure. There is growing interest in these nanomaterials, due to their biocompatibility, potential applications and availability. The surface chemistry of HNTs is versatile for the targeted chemical modification of the inner lumen and outer surface. Functionalized halloysite constitutes a valuable support for metal nanoparticles, promoting catalytic applications with tunable properties. The peculiar tubular shape of HNTs favors the dispersion and surface availability of the supported metal nanoparticles that are active in the catalytic path. Moreover, the presence of an empty lumen opens new perspectives for the prod…

A preliminary study on anion binding ability of geminal diimidazolium salts

Materiali ibridi a base di nanotubi di allosite per la rimozione d’inquinanti

L’allosite (HNT) è un interessante materiale argilloso allumino-silicato naturale, non tossico e biocompatibile, con la caratteristica forma tubolare cava dotata di parziale carica positiva interna e negativa esterna.Combinando le peculiarità di un composto organico con le proprietà di un materiale inorganico, è possibile ottenere sistemi ibridi organici–inorganici con interessanti proprietà e vasti campi di applicazione. Sono un esempio delle “nanospugne” capaci di adsorbire efficacemente potenziali inquinanti. In questo contesto sono stati preparati, dei materiali ibridi “spugna” costituiti da unità ciclodestriniche e allosite e ancora un sistema ibrido HNT-Cucurbit[8]uril. Il primo possi…

Effect of ionic liquids in acid-promoted heterocyclic rearrangement reaction

Recyclable organocatalysts

Ionic Liquids: as the different structural order degree can affect the outcome of a reaction

Oxidative cyclization of aldehyde thiosemicarbazones induced by potassium ferricyanide and by tris(p-bromophenyl)amino hexachloroantimoniate. A joint experimental and computational study

The oxidative ring closure reaction of some aryl-substituted thiosemicarbazones induced by "bona fide" one-electron abstracting agents was investigated, by means of both experimental and computational techniques. The corresponding 1,2,4-triazole derivatives were the only cyclization products observed. The occurrence of two slightly different mechanistic pathways for the reaction is discussed.

Acidic imidazolium salts: catalysts for biomass transformation

Spectrophotometric determinations of binding constants between cyclodextrins and aromatic nitrogen substrates at various pH values

The inclusion capacity of native β-cyclodextrin (1) and mono-(6-amino-6-deoxy)-β-cyclodextrin (2) versus aromatic compounds having a nitro or an amino group or both has been investigated at three different pH values. Molecular interactions in inclusion complexes have also been investigated by means of molecular mechanics (MM2/QD) models. Electrostatic and van der Waals interactions and the formation of a hydrogen bond between the donor amino group and the oxygen atom of the secondary hydroxyl group seem to be the more important contributions in determining complex stability. The inclusion capacity of two different cyclodextrins versus aromatic compounds has been investigated at three differ…

Halloysite Nanotubes: Smart Nanomaterials in Catalysis

The use of clay minerals as catalyst is renowned since ancient times. Among the different clays used for catalytic purposes, halloysite nanotubes (HNTs) represent valuable resources for industrial applications. This special tubular clay possesses high stability and biocompatibility, resistance against organic solvents, and most importantly be available in large amounts at a low cost. Therefore, HNTs can be efficiently used as catalysts themselves or supports for metal nanoparticles in several catalytic processes. This review reports a comprehensive overview of the relevant advances in the use of halloysite in catalysis, focusing the attention on the last five years.

Synthesis of 2,4,6-trisubstituted tetrahydropyrans via 6-exo selenoetherification of unsaturated alcohols

Stereoselectivity, regioselectivity and yields in the 6-exo selenoetherification of four unsaturated diols were found to depend on the stereochemistry of the diols and on the presence of an oxygen atom close to the intermediate seleniranium ring. Silica gel was useful in order to obtain good yields. Reactions performed both under kinetic and thermodynamic control led to the same products. Stereoselectivity, regioselectivity and yields in the 6-exo selenoetherification of four unsaturated diols were found to depend on several factors such as the stereochemistry of the diols, the nature of the R group, the nature of the counter anion of the PhSe+ species and the presence of silica gel.

Selective functionalization of halloysite cavity by click reaction: structured filler for enhancing mechanical properties of bionanocomposite films

Selective modification of the inner surface of halloysite nanotubes (HNTs) by the cycloaddition of azides and alkynes (click reaction) was successfully achieved. Fourier transform infrared spectroscopy and thermogravimetry confirmed that the modification involved only the HNT cavity. Morphological investigations evidenced that the functionalized nanotubes formed microfibers and clusters in the micrometer range. By means of the casting method, these nanomaterials were dispersed into biopolymeric matrixes (chitosan and hydroxypropyl cellulose) with the aim of obtaining nanocomposite films with tunable properties from the physicochemical viewpoint. For comparison purposes, we also characterize…

DICATIONIC IMIDAZOLIUM SALTS: TUNABLE ANTIMICROBIAL AND ANTITUMORAL CHEMIOTHERAPEUTIC LEADS

The chemical synthesis of novel chemotherapeutical leads is evolving thanks to possibility to design molecules with desired physical-chemical and, thus, biological properties. The imidazolium salts, recently proven effective to inhibit bacterial and/or cancer cell growth, posses an amphiphilic nature that is conferred by the imidazolium cation having a polar head generally coupled with aliphatic side chains. Thus, biological properties of imidazolium salts can be tuned through modifications involving the cation structure and/or the anion nature. By covalently linking two imidazolium rings, di-imidazolium salts were obtainedobtain differing in: i) kind of anions; ii) geometric isomerization …

Methylation of 2-phenylamino-1,3,4-thiadiazole. A structure debated

The true identity of the 4-methyl-5-phenylimino-δ2-1,3,4-thiadiazoline (A) has been demonstrated. The reactions, previously reported in the literature to give A have been repeated and the structure of the compounds obtained has been established.

Covalently modified halloysite clay nanotubes: synthesis, properties, biological and medical applications

Halloysite (HNT) is a promising natural nanosized tubular clay mineral that has many important uses in different industrial fields. It is naturally occurring, biocompatible, and available in thousands of tons at low cost. As a consequence of a hollow cavity, HNT is mainly used as nanocontainer for the controlled release of several chemicals. Chemical modification of both surfaces (inner lumen and outer surface) is a strategy to tune the nanotube's properties. Specifically, chemical modification of HNT surfaces generates a nanoarchitecture with targeted affinity through outer surface functionalization and drug transport ability from functionalization of the nanotube lumen. The primary focus …

Mononuclear rearrangements of heterocycles in water/β-CD: information on the real site of reaction from structural modifications of substrates and from proton concentration dependence of the reactivity

Abstract The effect of β-cyclodextrin (β-CD) on the reactivity in the base-catalyzed pathway for the rearrangement in water of some ( Z )-hydrazones of 3-benzoyl-1,2,4-oxadiazoles ( 1b – f ) into the relevant triazoles ( 2b – f ) was investigated, finding different behavior as a function of the proton concentration. ESIMS and 1 H NMR data evidence the formation of host – guest complexes. The whole of the experimental and calculated (MM2) data enabled us to draw some intriguing conclusions concerning the influence of the structures of the substrates and the nature of the formed host – guest complexes on the real site of the reaction.

Kemp elimination: a probe reaction to study ionic liquids properties.

The amino induced elimination of benzisoxazole into the relevant o-cyanophenolate ion (Kemp elimination) has been studied in [bmim][BF 4] solution at 298 K. To have information about the interactions between reactants and ionic liquid, the reaction has been carried out at different temperatures (293-313 K). Several primary, secondary, and tertiary amines have been used to study the effect of amine structure on the reaction rate. The collected data show that the amine structure seems to have a crucial role in determining the reaction rate. Furthermore, as different cation or anion structures of an ionic liquid can significantly affect its properties, the title reaction has been performed in …

As the change in ternary agent structure influence the chiral recognition ability of pyrene/heptakis-(6-amino)-(6-deoxy)-b-cyclodextrin

Advances towards highly active and stereoselective simple and cheap proline-based organocatalysts

Ten 4-acyloxy-L-prolines were screened as catalysts at loadings of 2–0.1 mol-% for the direct asymmetric aldol reaction in water by using variable amounts of water. Among them, a new catalyst, the L-proline carrying a trans-4-(2,2-diphenylacetoxy) group, and a catalyst previously synthesized by us, the L-proline carrying a trans-4-(4-phenylbutanoyloxy) group, were found to be excellent catalysts for the aldol reaction between cyclohexanone or cyclopentanone and substituted benzaldehydes when employed in only 1 and 0.5 mol-%,respectively, at room temperature without additives. For such catalysts, high turnover numbers were obtained, which are among the highest values obtained for enamine org…

Ionic liquid binary mixtures: Promising reaction media for carbohydrate conversion into 5-hydroxymethylfurfural

Abstract The conversion of carbohydrates into 5-hydroxymethylfurfural (5-HMF) has been studied in binary mixtures of ionic liquids (ILs), using strongly acidic resin Amberlyst 15 as the catalyst. In particular, both mono- and disaccharides, such as fructose, glucose and sucrose have been investigated. Considering the favorable effect exerted by chloride-based ionic liquids in the dissolution of carbohydrates, we used binary mixtures of 1-butyl-3-methylimidazolium chloride ([bmim][Cl]) with [bmim + ] based ionic liquids differing in size, shape and coordination ability of the anion ([bmim][BF 4 ], [bmim][N(CF 3 SO 2 ) 2 ], [bmim][N(CN) 2 ], [bmim][SbF 6 ] and [bmim][CF 3 SO 3 ]). Carbohydrat…

A study of the mechanism of the oxidative cyclization of benzaldehyde semicarbazones induced by cupric perchlorate in acetonitrile

Treatment of benzaldehyde semicarbazones 1a-i with cupric perchlorate in acetonitrile at 40 provided selectively the corresponding 1,2,4-triazolin-5-ones 2a-i. The relative rate constants for 2a-i formation were determined by the competitive method. The results obtained showed that electron-donating substituents (methyl and methoxy) increase the reaction rate, while the reverse was found for electron-withdrawing substituents (chloro and nitro group). The reactivity data are discussed on the grounds of two possible mechanisms.

Polystyrene-supported proline and prolinamide. Versatile heterogeneous organocatalysts both for asymmetric aldol reaction in water and α-selenenylation of aldehydes

A simple and efficient synthesis of polystyrene-supported proline and prolinamide has been carried out. Polystyrene-supported proline has been used as organocatalyst in the asymmetric aldol reaction between cyclohexanone and substituted benzaldehydes in water without any additive. High yields, diastereoselectivities and ee values have been observed. The versatility of this resin was demonstrated in the α-selenenylation of aldehydes. Both proline and prolinamide resins gave high yields. Recycling studies showed that the proline resin gave better results than prolinamide resin.

Sol-gel entrapped chromium(VI): a new selective, efficient and recyclable oxidizing system

Abstract The sol-gel entrapment of chromium(VI) within a silica matrix, obtained by oxidation with ozone of the corresponding entrapped chromium(III), was found to be an efficient and recyclable oxidizing system (at least up to 16 times) for benzylic alcohols. No leaching of chromium in solution was observed, which prevented any environmental pollution.

Novel prolinamide-supported polystyrene as highly stereoselective and recyclable organocatalyst for the aldol reaction

A new prolinamide derivative anchored to a polystyrene support has been straightforwardly prepared and employed as heterogeneous catalyst in the direct asymmetric aldol reaction with good results in terms of yield and stereoselectivity. The optimal reaction conditions were found when a 1:2 (v/v) water/chloroform mixture was used. This mixture was the best compromise between the good swelling properties of chloroform and the formation of a concentrated organic phase due to the presence of water. Noticeably, the enantioselectivities obtained employing acetone as ketone were, to the best of our knowledge, the highest achieved with a supported proline derivative. This catalyst can be easily rec…

Self-assembly process of diimidazolium salts: the effect of the alkyl chain length and isomeric substitution

Photochemical cyclization of some aldehyde thiosemicarbazones

The photochemical behaviour of some substituted aldehyde thiosemicarbazones 1a-k has been investigated in methanol at 254 nm. Thiosemicarbazones of glyoxil methyl ester 1a-f cyclized to furnish the 3-thioxo- 1,2,4-triazin-5-one 2 ring system. The remaining thiosemicarbazones 1g-j gave 1,2,4-triazoline 4 derivatives.

Chiral recognition of protected amino acids by means of fluorescent binary complex pyrene/heptakis-(6-amino)-(6-deoxy)-β-cyclodextrin

The ability of the binary complex pyrene (Py)/heptakis-(6-amino)-(6-deoxy)-β-cyclodextrin (am-β-CD) to act as a chiral selector was tested at two pH values (8.0 and 9.0). Phenylalanine (Phe), methionine (Met) and histidine (His) were used as chiral model molecules. The stability of ternary complexes Py/am-β-CD/amino acid was determined by means of spectrofluorimetric measurements. The data collected showed an increase in stability going from the binary to ternary complex and above all the possibility to use the binary complex as a chiral selector. Finally, data collected at two pH values showed that the binary complex is a better chiral selector when charged rather than in its neutral form.

Self-assembly of a fluorescent diimidazolium naphthalene diimide salt: the effect of increasing alkyl chain length

Polystyrene-supported organocatalysts for α-selenenylation and Michael reactions

Abstract Three different resin-supported catalysts have been prepared by using the well established post-modification approach by means of thiol-ene coupling reaction. Two catalysts were tested for the first time in the asymmetric α-selenenylation of propanal, while the third catalyst was used in the Michael addition reaction. While the preliminary results are not encouraging in the case of supported Jorgensen’ catalyst, interesting data have been collected with both for the supported MacMillan and prolyl-prolinol catalysts. In fact, these catalysts displayed good activity and selectivity. A reversed enantioselectivity in the α-selenenylation was observed by changing the polarity of the sol…

IBRIDI FORMATI DA NANOTUBI DI CARBONIO A PARETE MULTIPLA E ESTERI FOSFORICI: PROPRIETA’ E STUDI STRUTTURALI

Nel corso degli ultimi anni i nanotubi di carbonio in virtù delle loro proprietà fisiche, chimiche e meccaniche sono diventati tra i più promettenti materiali per la realizzazione di congegni a livello nanometrico. I CNT trovano numerose applicazioni nel campo, della nanoelettronica, nella costruzione di materiali ad elevata conducibilità elettrica ed elevata resistenza meccanica,2 e vengono, anche, impiegati come agenti di rinforzo dispersi in una matrice polimerica.3 Problema principale di questi materiali è che essi risultano scarsamente solubili in ambiente acquoso e in solventi organici, a causa delle forti forze attrattive di van der Waals che esistono tra le superfici dei CNT, che li…

On the behaviour of the (Z)-Phenylhydrazones of some 5-alkyl-3-benzoyl-1,2,4-oxadiazoles in solution and in the gas phase: kinetic and spectrometric evidence in favour of self-assembly

Abstract Rate constants, k A,R , for the rearrangement of the ( Z )-phenylhydrazones ( 1a – e ) of a series of 5-alkyl-3-benzoyl-1,2,4-oxadiazoles substituted at C(5) with linear alkyl chains of different length (from C 4 up to C 12 ) into the relevant 4-acylamino-2,5-diphenyl-1,2,3-triazoles ( 2a – e ) have been measured in dioxan/water in the base-catalyzed region (pS + 10.5–12.6). For each substrate log  k A,R are linearly related to pS + . The significant decrease of the slopes of these straight lines (from 0.96 down to 0.78) upon increasing the length of the linear alkyl chain at C(5) and that of the reactivity (down to 14–26%) upon increasing the substrate concentration suggest a decr…

Alkyl chain length effect on the self assembly of diimidazolium naphthalene diimide salts

Sequential Suzuki/Asymmetric Aldol and Suzuki/Knoevenagel Reactions Under Aqueous Conditions

Here we describe for the first time a sequential Suzuki/asymmetric aldol reaction. Such sequential approach was achieved through the combined use of an ionic liquid supported palladium catalyst and the organocatalyst trans-4-(2,2-diphenylacetoxy)proline. Suzuki and asymmetric aldol reactions were performed under aqueous conditions. The use of a palladium catalyst under basic conditions allowed also the first example of sequential Suzuki/Knoevenagel reaction. Reactions were carried out under aqueous conditions and products were isolated in good to high yields and, in the case of the Suzuki/aldol reaction, with diastereoselectivities up to 91:9 and enantioselectivities up to at least 99 %.

The effect of ionic liquids on the rate of an intramolecular nucleophilic substitution: the study of a monocyclic rearrangement of heterocycles

Gas-phase and solution basicities of some alkyl 2,6-dialkylphenyl ketones: A comparative analysis

Abstract The gas-phase basicity of a number of alkyl 2,6-dialkylphenyl ketones (2,6-R2C6H3COR′) has been found to be almost insensitive to structural variations, as a result of a compensation of steric and electronic effects associated with the bulkiness and to the polarizability, respectively, of R and/or R′. On the contrary, the basicity in concentrated sulfuric acid undergoes, along the same series of compounds, a variation of nearly 8 pK units, as a consequence of steric inhibition of solvation of the protonated carbonyl as the main effect played by R and/or R′. The results in the condensed phase agree very nicely with recent findings relevant to some 4-substituted 2,6-dimethylacetophen…

Short and efficient chemoenzymatic synthesis of goniothalamin

Silver nanoparticles stabilized by a polyaminocyclodextrin as catalysts for the reduction of nitroaromatic compounds

Abstract Silver nanoparticles stabilized by means of poly -(6- N , N -dimethyl-propylenediamino)-(6-deoxy)-β-cyclodextrin were synthesized, characterized by different techniques (UV–vis spectroscopy, Dynamic Light Scattering, High Resolution Transmission Electron Microscopy, Fourier-transform IR Spectroscopy) and used as catalysts for the reduction of various nitrobenzene derivatives with sodium borohydride. The nanocomposites obtained appear to have an organized structure, with a metal core surrounded by a layer-structured coating shell. Kinetic data, rationalized in terms of a modified Langmuir–Hinshelwood model, evidenced a non-linear dependence of the reaction rate on the concentration …

Two components hydrogels formed by host-guest interactions

The ionic liquid effect on the Boulton-Katritzky reaction: a comparison between substrates of different structure

The mononuclear rearrangement of heterocycles, also called Boulton–Katritzky reaction, was studied in ionic liquid solution using N-(5-phenyl-1,2,4-oxadiazol-3-yl)-N′-(4-nitrophenyl)-formamidine as substrate. The investigation was carried out using piperidine as basic catalyst and several ionic liquids differing in both cation and anion structure. Kinetic data collected were compared with the ones previously reported using (Z)-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole to have information about the effect due to the different structure of the alkyl chain borne on the substrate. Furthermore, data were analysed on the grounds of polarity, Kamlet–Taft solvent parameters, but taking…

FUNZIONALIZZAZIONE E CARATTERIZZAZIONE DI NANOTUBI DI ALLOSITE UTILIZZATI PER LO STUDIO DELL’INCAPSULAMENTO DI DERIVATI FENOLICI

I composti fenolici fanno parte dei metaboliti secondari delle piante e tra questi la curcumina è stata ampiamente studiata per le sue intrinseche proprietà farmacologiche.1-4 La curcumina [bis(4-idrossi-3-metossi-fenil)-1,6-eptadiene-3,5-dione] isolata sotto forma di pigmento giallo dal rizoma secco della curcuma longa è stata utilizzata in presenza di sistemi delivery per applicazioni farmaceutiche.5 Uno degli svantaggi della curcumina è la sua scarsa biodisponibilità in ambiente acquoso;6 problema che può essere risolto incapsulandola in nanocontenitori. Tra i sistemi nanodelivery naturali che non presentano citotossicità vi sono i nanotubi di allosite. I nanotubi di allosite sono…

Binding properties of polyaminocyclodextrin materials towards polyanions and p-nitroaniline derivatives

Halloysite Nanotubes as Support for Metal-Based Catalysts

Halloysite nanotubes (HNTs) are a natural, biocompatible, environmental friendly and cheap double-layered aluminosilicate mineral that has a predominantly hollow tubular structure. The general stoichiometry of halloysite is Al2Si2O5·4(H2O). The layer units consist of a tetrahedral SiOH sheet stacked with an edge shared octahedral AlO6 sheet with an internal aluminol group AlOH. A water layer exists between the adjacent two layers. Thanks to their structural features, HNTs are suitable for a potential application as support for catalytic composites. Recently, we reported the synthesis of novel palladium-based catalytic systems using halloysite nanotubes modified with imidazolium or triazoliu…

A kinetic study of the basic hydrolysis of 2-phenylethyl nitrite in the presence of borate buffer and β-cyclodextrin

The kinetics of the hydrolysis of 2-phenylethyl nitrite have been studied in basic aqueous solutions (borate buffer) in the absence and presence of β-cyclodextrin. The observed kinetic trends show that the hydrolysis reaction consists of at least three subsequent processes. The first is a fast acid-base reaction between the boron atom of boric acid and oxygen atom of the alkyl nitrite. The second one should be the nucleophilic attack of hydroxyl ion on the alkyl nitrite. The last process could be referred to as a combination of transfer of hydrogen acid to a water molecule followed by ruptures of nitrogen-oxygen and boron-oxygen bonds. The effect of β- cyclodextrin on each process is also d…

Diimidazolium-based supramolecular ionogels for dye removal from wastewaters

Beta-cyclodextrin as host for the rearrangement of some Z-hydrazones of 3-benzoyl-5-X-1,2,4-oxadiazoles.

Green conditions for the Suzuki reaction using microwave irradiation and a new HNT-supported ionic liquid-like phase (HNT-SILLP) catalyst

A new catalytic system based on modified halloysite nanotubes was employed in the Suzuki reaction under microwave irradiation. A set of solvents, times and bases was screened and the best experimental conditions were obtained when the reactions were carried out for 10 min in water–ethanol at 120 °C in presence of K2CO3 as base. Good recyclability was observed. The new catalytic system was employed using either 1 mol% or 0.1 mol%. The palladium catalyst displayed good activity, allowing the synthesis of several biphenyl compounds in high yield working with only 0.1 mol% palladium loading. The application of microwave irradiation decreased the reaction time and also improved conversion with r…

Recyclable Catalyst Reservoir: Oxidation of Alcohols Mediated by Noncovalently Supported Bis(imidazolium)-Tagged 2,2,6,6-Tetramethylpiperidine 1-Oxyl

Bis(imidazolium)-tagged 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) catalysts were adsorbed on different supports such as silica gel, silica gel modified with highly cross-linked polymeric imidazolium networks, and highly cross-linked polymeric imidazolium networks entrapping magnetic particles. These systems provided a convenient tool for the oxidation of both primary and secondary alcohols working as recyclable reservoirs for the bis(imidazolium)-tagged TEMPO catalysts. By using EPR spectroscopy it was demonstrated that the catalyst was released as the corresponding oxoammonium salt in the solution during the recycling step, thus promoting the oxidative process in a homogeneous fashion. …

The ultrasounds-ionic liquids synergy on the copper catalyzed azide-alkyne cycloaddition between phenyl acetylene and 4-azidoquinoline

Abstract The effect of ultrasound irradiation on the copper catalyzed azide–alkyne cycloaddition between phenylacetylene and 4-azidoquinoline has been studied in solution of different ionic liquids. In particular, we used ionic liquids featuring both aliphatic and aromatic mono- and dications, as well as anions differing in size, symmetry and coordination ability. We also examined the influence of the ionic liquids structural features on the reaction outcomes, finding that under magnetic stirring reactivity is favorably affected by the solvent structural organization, while under sonochemical conditions an opposite trend was observed. In all cases examined, sonochemical activation leads to …

ChemInform Abstract: A Quantitative Study of Substituent Effects on Oxidative Cyclization of Some 2-Methylsubstituted Aldehydes. Thiosemicarbazones Induced by Ferric Chloride

In order to gain further mechanistical information about the cyclization of thiosemicarbazones and thiosemicarbazone-type substrates induced by metallic salts as oxidizing agents, we performed the synthesis of substrates 1a-s and a kinetic study of the oxidative cyclization of 1 to 5-imino-Δ2-1,3,4-thiadiazole 2 and 1,2,4-triazoline-5-thione 3 derivatives induced by methanolic ferric chloride solutions. The results of cyclization were compared to those of corresponding semicarbazones. The kinetic data were analyzed by means of the Hammett's equation and ρ values discussed.

Polystyrene-supported proline as recyclable catalyst in the Baylis–Hillman reaction of arylaldehydes and methyl or ethyl vinyl ketone

Abstract Polystyrene-supported proline has been used as co-organocatalyst (10 mol%) with imidazole (10 mol%) in the Baylis–Hillman reaction between methyl or ethyl vinyl ketone and arylaldehydes. Recycling studies showed that the proline resin can be used up to five cycles with high isolated yields. This study represents the first example of supported proline as heterogeneous catalyst in the above reaction and broaden the scope of this catalytic material.

Binding properties of mono-6-amino-beta-cyclodextrin towards p-nitroaniline derivatives: a polarimetric study

Aryl azides formation under mild conditions: a kinetic study in some ionic liquid solutions.

The kinetics of nucleophilic aromatic substitution of three nitrothiophene derivatives in different [1-butyl-3-methylimidazolium][N(3)]/ionic liquid binary mixtures was studied spectrophotometrically at 298 K. Ionic liquids differing for cation structure (imidazolium or pyrrolidinium) and for size, shape, and coordination ability of the anion ([BF(4)(-)], [PF(6)(-)], [SbF(6)(-)], and [NTf(2)(-)]) were used. Furthermore, in order to have a comparison with conventional organic solvents, the target reaction was also carried out in DMF solution at increasing concentration of NaN(3) or [bmim][N(3)]. Data collected show that the reaction occurs faster in DMF than in ionic liquid solution. Further…

Palladium on pumice: new catalysts for the stereoselective semihydrogenation of alkynes to (Z)-alkenes

Abstract High selectivities (93–99%) and excellent stereoselectivities (>99%) in the semihydrogenation of CC triple bonds were achieved using palladium on pumice with a metal loading of 0.5, 1.5 or 3.0% wt as catalyst. The reactions were carried out in ethanol or tetrahydrofuran with only 2.5% of ethylenediamine allowing a self-terminating semihydrogenation independently on the CC triple bond.

Insights into the anion effect on the self assembly of perylene bisimide diimidazolium salts

Abstract We studied how changing the anion affects the self-assembly of three diimidazolium salts bearing a perylene bisimide spacer. In particular we used [BF 4 − ] and [NTf 2 − ] based salts together with a mixed salt bearing both [I − ] and [BF 4 − ] anions. Thermal as well as concentration and temperature dependent spectroscopic investigations revealed that changing the anion impacts on solid state and solution aggregation, leading to articulate thermotropic behaviors and contrasting solvent effects, respectively. We also studied the electrochemical behavior of the salts to verify if changing the anion alters the redox properties of the salts. Finally, different anions also lead to very…

Photochemical preparation of polyaminocyclodextrin-capped silver nanocomposites: mechanistic insights

Photoreduction of silver salts in the presence of three polyaminocyclodextrin derivatives (AmCD, Figure 1) constitutes a simple and straightforward route to obtain stable Ag nanoparticles. These systems have been suitably characterized (UV-vis, FT-IR, TEM, Figure 2) and tested for their antimicrobial activity.1 We observed that Ag photoreduction is effectively induced by irradiation with green light (513 nm); however, best performances are achieved with the use of a light source having at the same time a significant emission in the near-infrared (NIR) region. On the grounds of analytical and kinetic evidences, we hypothesized a multi-step mechanism for nanoparticle formation. In particular,…

Enhanced Activity and Stereoselectivity of Polystyrene-Supported Proline-Based Organic Catalysts for Direct Asymmetric Aldol Reaction in Water

Several polystyrene-supported proline dipeptides and a prolinamide derivative were prepared by thiol–ene coupling. These materials were used as catalysts for the direct asymmetric aldol reaction in water, and results compared with unsupported catalysts in water. Such an approach gave more active or stereoselective catalysts compared to the unsupported compounds, showing that our immobilization procedure may be useful to develop catalytic materials with enhanced performance. Moreover, these catalysts can be recovered and reused for at least nine times without loss of activity or can be easily regenerated when their activity has decreased. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, …

ChemInform Abstract: Palladium on Pumice: New Catalysts for the Stereoselective Semihydrogenation of Alkynes to (Z)-Alkenes.

Abstract High selectivities (93–99%) and excellent stereoselectivities (>99%) in the semihydrogenation of CC triple bonds were achieved using palladium on pumice with a metal loading of 0.5, 1.5 or 3.0% wt as catalyst. The reactions were carried out in ethanol or tetrahydrofuran with only 2.5% of ethylenediamine allowing a self-terminating semihydrogenation independently on the CC triple bond.

Interazioni non covalenti tra esteri fosforici e nanotubi di carbonio a parete multipla

Fin dal 1991, quando Iijima li osservò per la prima volta, i nanotubi di carbonio (CNT) sono diventati oggetto d'interesse scientifico, in virtù delle loro proprietà fisiche, chimiche e meccaniche. Un impiego molto interessante riguarda l'aumento di stabilità di matrici polimeriche. I nanocompositi polimerici, in cui sono presenti percentuali molto basse di CNT (2.5%), presentano enormi miglioramenti nelle caratteristiche termomeccaniche, nella resistenza al calore e nella conduttività elettrica. C'è, però, un impedimento fondamentale a tutte le applicazioni che riguarda l'insolubilità intrinseca dei CNT nei solventi. La funzionalizzazione sia essa covalente che non è un espediente per ovvi…

Determination of basic strenght of aliphatic amines through ion pair formation in some ionic liquid solutions

To have an evaluation of the basic strength of aliphatic amines in ionic liquid solution, the stability constants relevant to the formation of amine/p-nitrophenol ion pairs were determined in different ionic liquids at 298 K. In particular, aliphatic (pyrrolidinium) and aromatic (imidazolium) ionic liquids were used. Imidazolium ions, bmim(+) and bm(2)im(+), having different hydrogen bond donor abilities were taken into account. Anions were chosen ([BF(4)(-)], [PF(6)(-)], and [NTf(2)(-)]; where NTf(2) = bis(trifluoromethansulfonyl)imide) showing different shape, size, and coordination ability. Several primary, secondary (cyclic or not), and tertiary amines were used to study the effect of a…

Host−Guest Interactions between β-Cyclodextrin and the (Z)-Phenylhydrazone of 3-Benzoyl-5-phenyl-1,2,4-oxadiazole:  The First Kinetic Study of a Ring−Ring Interconversion in a “Confined Environment”

The effect of beta-cyclodextrin (beta-CD) on the mononuclear heterocyclic rearrangement of the (Z)-phenylhydrazone of 3-benzoyl-5-phenyl-1,2,4-oxadiazole (1) in aqueous borate buffer at pH = 9.6 has been analyzed at temperatures ranging from 293.15 to 313.15 K. The trend of the absorption spectra of 1 as a function of time has been accounted for with the formation of two different 1:1 complexes between beta-CD and 1, the first, "unreactive" complex being formed faster than the "reactive" one. The occurrence of negative activation enthalpy values for the studied interconversion evidences the kinetic relevance of inclusion processes. Computational models elaborated using the MM2 molecular mec…

Chromia on silica and zirconia oxides as recyclable oxidizing system: structural and surface characterization of the active chromium species for oxidation reaction

Chromium oxide samples supported over silica and zirconia were prepared by wet impregnation of the supports with aqueous solution of CrO3. In order to investigate the influence of the preparation method on the chromium dispersion and oxidation state, one sample was prepared by sol-gel technique. The materials were structurally characterized by XRD analysis. The oxidation states of chromium species were investigated by XPS, DRS and TPR/TPO techniques. EPR analyses were also carried out for the sample Cr/SiO2, that due to the low crystalline state exhibits broad XPS signals. In this case, particular attention was paid to the presence of Cr(V) and Cr (III) species and their concentration. The …

Spectrophotometric determination of binding constants between some aminocyclodextrins and nitrobenzene derivatives at various pH values

Abstract The inclusion capacity of three modified cyclodextrins—namely mono-(6- N , N -dimethylamino-6-deoxy)- ( 3 ), mono-6-(2-aminoethyl)-amino-6-deoxy- ( 4 ) and mono-6-(2- N , N -dimethylaminoethyl)-amino-6-deoxy- ( 5 ) β-cyclodextrin, with six para -substituted nitrobenzenes ( A – F ) has been investigated at three different pH values. Molecular interactions in inclusion complexes have also been investigated by means of molecular mechanics (MM2/QD) models. The desolvation of the cyclodextrin is the most important factor in determining the binding ability of the various hosts. However, for a given host, electrostatic and van der Waals interactions and the formation of a hydrogen bond be…

Fully ionic metallogels from dicationic diimidazolium salts

Binary complexes heptakis-(6-amino)-(6-deoxy)-beta-cyclodextrin/fluorophore: structural investigation and chiral recognition

Inside Back Cover: Aggregation Processes of Perylene Bisimide Diimidazolium Salts (Chem. Eur. J. 42/2015)

Self-assembly of fluorescent diimidazolium salts: tailor properties of the aggregates changing alkyl chain features

Searching for new fluorescent organic salts to be used in biomedical and electrochemical field, we conjugated properties of imidazolium salts with the ones of naphthalene diimide core and we obtained some N,N′-bis-(1-alkyl-3-propylimidazolium)naphthalene diimide diiodides. We took into account alkyl chains going from hexyl to dodecyl, as well as hydrogenated and fluorinated alkyl tails. After determination of their thermal behaviour by differential scanning calorimetry, concentration-, and temperature-dependent spectroscopic studies (UV-vis and fluorescence) were performed evidencing the occurrence of isodesmic and enthalpy-driven self-assembly processes. Properties of aggregates were also …

Dicationic organic salts: gelators for ionic liquids

Diimidazolium and dipyrrolidinium organic salts were tested for their ability to gel both organic solvents and ionic liquids. Organic salts containing 1-(1-imidazolylmethyl)-3,5-di-(3'-octylimidazolylmethyl)-benzene and 1-(N-pyrrolidylmethyl)-3,5-di-(N,N-octylpyrrolidylmethyl)-benzene cations were used. In addition to the simple bromide anion, also dianions having a naphthalene core such as 1,5- and 2,6-naphthalenedisulfonate and 2,6-naphthalenedicarboxylate were taken into account. Gelation tests demonstrated that organic salts used were able to harden ionic liquids. The materials obtained were investigated for their thermal stability and also for electric conductivity properties using mic…

ChemInform Abstract: New Simple Hydrophobic Proline Derivatives as Highly Active and Stereoselective Catalysts for the Direct Asymmetric Aldol Reaction in Aqueous Medium.

New 4-substituted acyloxyproline derivatives with different hydrophobic properties of the acyl group were easily synthesized and used as catalysts in the direct asymmetric aldol reaction between cyclic ketones (cyclohexanone and cyclopentanone) and several substituted benzaldehydes. Reactions were carried out using water, this being the best reaction medium examined. Screening of these catalysts showed that compounds bearing the most hydrophobic acyl chains [4-phenylbutanoate and 4-(pyren-1-yl)butanoate] provided better results. The latter catalysts were successfully used in only 2 mol% at room temperature without additives to give aldol products in excellent stereoselectivities. These resu…

FUNZIONALIZZAZIONE DELLA SUPERFICIE DELL’ALLOSITE MEDIANTE RISCALDAMENTO A MICROONDE

L’allosite (Al2Si2O5•2H2O), è un alluminosilicato naturale, chimicamente simile al caolino; essa ha una struttura tubolare cava dell’ordine dei micrometri (0.5-1 μm ) e un diametro interno dell’ordine dei nanometri (15 nm ). I nanotubi di allosite (HNT) presentano sulla superficie esterna gruppi SiO2 mentre su quella interna gruppi AlOH. Viste le caratteristiche strutturali, HNT trovano applicazioni come Host, fungendo in alcuni casi da nanoreattori. Tali applicazioni sono però limitate dall’idrofilia della superficie, sia interna che esterna. In questo lavoro è stata sviluppata una nuova metodologia sintetica che prevede l’ultilizzo delle microonde per ancorare organosilani come precursori…

Effetto della struttura dei liquidi ionici sulla reazione di trasposizione eterociclica mononucleare: un approccio usando i parametri termodinamici

Lipase-catalyzed resolution of β-hydroxy selenides

Abstract Eleven β-hydroxy selenides were kinetically resolved using an immobilized lipase (Amano PS-C II) in toluene in the presence of vinyl acetate at 30 °C. This approach provided, in several cases, both enantiomers in high enantiomeric excess. The role of the size of substituents and the behaviour of cyclic β-hydroxy selenides is also discussed. Enantiopure β-hydroxy selenides are useful building blocks. As an application of this chemistry, enantiopure (1 S ,2 R )-indene oxide was obtained in one step from the proper enantiopure β-hydroxy selenide.

Chemical modification of halloysite nanotubes for controlled loading and release.

Clay minerals have been used for medical purposes from ancient times. Among them, the halloysite nanotube, an aluminosilicate of the kaolin group, is an emerging nanomaterial which possesses peculiar chemical characteristics. By means of suitable modifications, such as supramolecular functionalization or covalent modifications, it is possible to obtain novel nanomaterials with tunable properties for several applications. In this context the covalent grafting of suitable organic moieties on the external surface or in the halloysite lumen has been exploited to improve the loading and release of several biologically active molecules. The resulting hybrid nanomaterials have been applied as drug…

Caratterizzazione e valutazione dell’attività anti proliferativa di nuovi sistemi per il drug carrier Allosite-sali triazolici/cardanolo

Da precedenti studi è stato valutato che i nanotubi di allosite modificati con sali triazolici (f-HNT), sono dei promettenti sistemi carrier per molecole biologiche1. In questo lavoro si riportano i risultati ottenuti studiando gli f-HNT come carrier per il cardanolo, molecola con interessanti attività biologiche. L’interazione fra il cardanolo e gli f-HNT è stata valutata tramite HPLC, spettroscopia FTIR, analisi termogravimentrica, misure di angolo di contatto e microscopia a scansione elettronica. Infine sono stati studiati sia il rilascio del cardanolo dal sistema che gli effetti citotossici del complesso f-HNT/Cardanolo verso linee cellulari di epatocarcinoma. I dati sperimentali otten…

How mixing ionic liquids affects a Diels-Alder reaction

Development and characterization of co-loaded curcumin/triazole-halloysite systems and evaluation of their potential anticancer activity.

Abstract Positively charged halloysite nanotubes functionalized with triazolium salts (f-HNT) were employed as a carrier for curcumin molecules delivery. The synthesis of these f-HNT new materials is described. Their interaction with curcumin was evaluated by means dynamic light scattering (DLS) and UV–vis spectroscopy in comparison with pristine unmodified HNT (p-HNT). The curcumin load into HNT was estimated by thermogravimetric analysis (TGA) measurements, while the morphology was investigated by scanning electron microscopy (SEM) techniques. Release of curcumin from f-HNT, at three different pH values, by means of UV–vis spectroscopy was also studied. Furthermore, different cancer cell …

Synthesis of aryl azides: A probe reaction to study the synergetic action of ultrasounds and ionic liquids

Abstract The combined effect of ultrasounds and ionic liquids was used to perform the synthesis of aryl azides by nucleophilic aromatic substitution in ionic liquid/[1-butyl-3-methylimidazolium][N 3 ] binary mixtures. The ultrasounds efficiency was analyzed as a function of the substrate and of the ionic liquid structure. In the first case, both 6π and 10π electrons aryl halides were considered. As far as the ionic liquid structure is concerned, both aromatic and aliphatic ionic liquids were taken into account. Among aromatic cations, the effects due to different ability in giving hydrogen bond or π–π interactions were considered. The use of a geminal ionic liquid having an aromatic spacer …

Simple and Cheap Highly Active Proline-Based Organocatalysts

[bmim][F] a TSIL differently acting on aromatic nuclei

Asymmetric Synthesis Using Polymer-Immobilized Proline Derivatives

N-heterocyclic carbenes and parent cations: acidity, nucleophilicity, stability, and hydrogen bonding-Electrochemical Study and ab initio calculations

N-Heterocyclic carbenes (NHCs) are widely used as organocatalysts. Their reactivity (and instability) is related to their basicity and nucleophilicity, which, in turn, are linked to their scaffold. NHCs can be generated by chemical deprotonation or electrochemical reduction of the parent azolium cations, NHCH+s. Cyclic voltammetry enabled the reduction potential of the NHCH+s to be determined; the reduction potential is related to the acidity of the NHCH+s and the oxidation potential of the NHCs, which is related to the nucleophilicity of the NHCs. It was thus possible to order different NHCH+s and NHCs by their acidity and nucleophilicity, respectively. A study on the stability of NHCs was…

L'assenza di solvatazione può giustificare l'aumento della velocità dei processi di interconversione di anello in liquidi ionici?

Microwave-assisted synthesis of novel cyclodextrin–cucurbituril complexes

Microwave irradiation was successfully used in order to obtain stable supramolecular aggregates between cyclodextrins and cucurbiturils, without the participation of any long-chain common ‘molecular thread’ guest. These aggregates were characterised by means of various different techniques, namely NMR, thermogravimetry, polarimetry and ESI-MS. Cross-analysis of experimental data allowed us to obtain insights on the stoichiometries of the composites and their thermal stabilities. The possible structures of the composites are briefly discussed, as well as the actual nature of their intrinsic stability.

ChemInform Abstract: Photochemical Cyclization of Some Aldehyde Thiosemicarbazones.

The photochemical behaviour of some substituted aldehyde thiosemicarbazones 1a-k has been investigated in methanol at 254 nm. Thiosemicarbazones of glyoxil methyl ester 1a-f cyclized to furnish the 3-thioxo- 1,2,4-triazin-5-one 2 ring system. The remaining thiosemicarbazones 1g-j gave 1,2,4-triazoline 4 derivatives.

NMR Spectroscopic characterization and thermal behaviour of a new class of dicationic imidazolium ionic liquids

Novel supported dipeptides as recyclable catalysts for asymmetric aldol reaction

Reazione di eliminazione di Kemp in liquidi ionici: uno studio cinetico

Functionalized halloysite multivalent glycocluster as a new drug delivery system.

A new design for halloysite nanotube materials was obtained by grafting chemically modified cyclodextrin units onto the nanotube surface. In particular, grafted cyclodextrins were decorated with thiosaccharide pendants, in order to mimic the well-known binding of sugars to proteins and the glyco-cluster effect occurring during cellular recognition events. The obtained materials were characterized by using a combination of varied techniques (FT-IR spectroscopy, thermogravimetric analysis, scanning electron microscopy, dynamic light scattering, turbidimetry), and their potential drug-delivery abilities were tested by studying their interactions with the common naturally occurring anticancer a…

Enantioselective recognition of alfa-amino acids by binary complexes fluorophore/cyclodextrin

Two-Component Hydrogels Formed by Cyclodextrins and Dicationic Imidazolium Salts

In the framework of our recent interest in studying the gelling behaviour of imidazolium salts, we took into account the possibility of obtaining two-component hydrogels by combining cyclodextrins and dicationic imidazolium salts. In particular, we used diimidazolium salts differing in the alkyl chain length and in the size, shape, and coordination ability of the anion, namely the 3,3′-di-n-decyl- and 3,3′-di-n-dodecyl-1,1′-(1,4- phenylenedimethylene)diimidazolium dibromide, and 3,3′-di-n-dodecyl-1, 1′-(1,4-phenylenedimethylene)diimidazolium ditetrafluoroborate and dihexafluorophosphate. As far as cyclodextrins are concerned, to gain information on the effects of different sized cyclic olig…

Studio polarimetrico degli equilibri di inclusione tra ciclodestrine native ed opportuni guest modello alifatici e aromatici

Ionic liquids/[bmim][N3] mixtures: promising media for the synthesis of aryl azides by SNAr

The nucleophilic aromatic substitution of some activated aryl or heteroaryl halides has been performed in ionic liquid solution, using the 1-butyl-3-methylimidazolium azide as a nucleophile. The reaction course was studied varying the structures of both substrates and ionic liquids. In particular, in the latter case, the reaction of 2-bromo-5-nitrothiophene was carried out in five different ionic liquids ([bmim][BF 4], [bmim][PF 6], [bmim][NTf 2], [bm 2im][NTf 2], and [bmpyrr][NTf 2]). Finally, for all the substrates considered, a comparison with data obtained in MeOH solution in the presence of NaN 3 was also performed. Data collected indicate that in some cases it is possible to obtain ar…

Short and Efficient Chemoenzymatic Synthesis of Goniothalamin.

A high-yielding three-step synthesis of goniothalamin involving an enzymatic kinetic resolution in the presence of vinyl acrylate followed by ring-closing metathesis is discussed.

Miscela binaria liquido ionico/[bmim][N3]: un mezzo efficace per la sintesi di arilazidi mediante SNAr

Direct asymmetric aldol reaction using polystyrene-supported proline amide

Kinetic study of methoxide-promoted elimination reactions of some 1,1,1-trichloro-2,2-bis(phenyl-substituted)ethanes

The methoxide-promoted elimination reaction of some 1,1,1-trichloro-2,2-bis(phenyl-substituted)ethanes (1) was investigated. The ortho-substituted derivatives were found to be less reactive than the corresponding ortho-unsubstituted derivatives, irrespective of the nature of their substituent. The reactivity data were correlated with the 13C NMR chemical shift values of C-β of either 1,1,1-trichloro-2,2-bis(phenyl-substituted)ethanes or 1,1-dichloro-2,2-bis(phenyl-substituted)ethenes and the better result was obtained for the former correlation. Activation parameters for the methoxide-promoted elimination of 1 show very similar values for ortho-substituted derivatives. The total data set se…

Linear free energyortho-correlations in the thiophene series. Part IX . Kinetics of esterification with diazodiphenylmethane of some 3-, 4-, and 5-substituted thiophene-2-carboxylic acids in methanol

The rate constants for the esterification of some 3-, 4-, and 5-substituted thiophene-2-carboxylic acids with diazodiphenylmethane in methanol at 25° have been measured. The reactivity of some para- and ortho-substituted benzoic acids has also been determined. Logarithmic kinetic constants for ortho-, meta-, and para-like substituted thiophene-2-carboxylic acids furnish an excellent linear free energy relationship when plotted versus Δpka (β 0.89, r 0.989, C.L. > 99.9%, n 18, i 0.04), thus confirming the peculiar behaviour of five-membered ring derivatives. The correlation with σH values offers an additional proof of the hyper-ortho character of the 2,3-relation in thiophene derivatives. pa…

Efficient microwave-mediated synthesis of fullerene acceptors for organic photovoltaics

Two different processes, namely the Bamford–Stevens and [4 + 2] Diels Alder reactions, have been optimized under microwave irradiation for the functionalization of fullerenes. In this manner, all the main C60- and C70-based acceptor derivatives for organic solar cells such as PCBM, DPM, BHN and ICBA, have been prepared in higher yields and shorter reaction times with respect to the reported data. These findings represent a step forward toward the wide production of cheaper organic solar cells as a consequence of the cost abatement of the acceptors given by higher yields, lower waste production, and reduced reaction time which means a strong energy saving.

New proline derivatives as recyclable catalysts for aldol reaction

ChemInform Abstract: Low-Loading Asymmetric Organocatalysis

Asymmetric organocatalysis is now recognized as the third pillar of asymmetric synthesis. Recent years have witnessed increasing interest towards the use of highly active and stereoselective organocatalysts. This critical review documents the advances in the development of chiral organocatalysts which are systematically used in ≤3 mol% loading in all the sub-areas of the field, namely aminocatalysis, Bronsted acids and bases, Lewis acids and bases, hydrogen bond-mediated catalysis, phase transfer and N-heterocyclic carbene catalyses (194 references).

ChemInform Abstract: Enhanced Activity and Stereoselectivity of Polystyrene-Supported Proline-Based Organic Catalysts for Direct Asymmetric Aldol Reaction in Water.

Several polystyrene-supported proline dipeptides and a prolinamide derivative were prepared by thiol–ene coupling. These materials were used as catalysts for the direct asymmetric aldol reaction in water, and results compared with unsupported catalysts in water. Such an approach gave more active or stereoselective catalysts compared to the unsupported compounds, showing that our immobilization procedure may be useful to develop catalytic materials with enhanced performance. Moreover, these catalysts can be recovered and reused for at least nine times without loss of activity or can be easily regenerated when their activity has decreased. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, …

Study of aromatic nucleophilic substitution with amines on nitrothiophenes in RTILs: are the different effects on the behavior of para-like and orto-like isomers on going from conventional solvents to RTILs related to solvation effects?.

The kinetics of the nucleophilic aromatic substitution of some 2-L-5-nitrothiophenes (para-like isomers) with three different amines (pyrrolidine, piperidine, and morpholine) were studied in three roomtemperature ionic liquids ([bmim][BF4], [bmim][PF6], and [bm2im][BF4], where bmim ) 1-butyl-3- methylimidazolium and bm2im ) 1-butyl-2,3-dimethylimidazolium). To calculate thermodynamic parameters, a useful instrument to gain information concerning reagent-solvent interactions, the reaction was carried out over the temperature range 293-313 K. The reaction occurs faster in ionic liquids than in conventional solvents (methanol, benzene), a dependence of rate constants on amine concentration sim…

MODIFICAZIONI COVALENTI DI NANOTUBI DI ALLOSITE PER APPLICAZIONE NEL DRUG DELIVERY

Nell'ampio scenario dei nanomateriali, i sistemi nanotubolari godono di un consolidato e crescente interesse sia nell'ambito scientifico che industriale. Fra la miriade di sistemi tubolari, recentemente i nanotubi allosite (HNT) hanno attirato l’attenzione della comunità scientifica.1 Grazie alla presenza di una cavità vuota, gli HNT trovano, principalmente, applicazione come nanocontainer per il rilascio controllato di composti chimici, in particolare, farmaci. L’introduzione di modificazioni covalenti su entrambe le superfici permette di modulare le proprietà dell’allosite, aumentando così i suoi campi di applicazione. In questa comunicazione verranno presentati recenti risultati ottenuti…

ChemInform Abstract: Recyclable Catalyst Reservoir: Oxidation of Alcohols Mediated by Noncovalently Supported Bis(imidazolium)-Tagged 2,2,6,6-Tetramethylpiperidine 1-Oxyl.

Biocompatible Poly(N-isopropylacrylamide)-halloysite Nanotubes for Thermoresponsive Curcumin Release

The grafting of poly(N-isopropylacrylamide) (PNIPAAM) onto the halloysite external surface is proposed in order to obtain a novel thermoresponsive drug carrier for curcumin delivery. The new nanomaterial is characterized by means of FT-IR spectroscopy, thermogravimetric analysis, and SEM investigations. A high density of polymer chain was achieved at the nanoparticle surface. The PNIPAAM dehydration phenomenon was observed in water above 32 °C that is nearly coincident with the lower critical solution temperature for the polymer. The colloidal stability as well as the wettability of the obtained nanomaterial may be triggered by temperature stimuli. In vitro tests simulating the gastro-intes…

Binding equilibria between beta-cyclodextrin and p-nitro-aniline derivatives: the first systematic study in mixed water-methanol solvent systems.

Abstract Complexation equilibria, in mixed water–methanol solvent media, between native β-cyclodextrin and a set of suitably selected p -nitro-aniline derivatives were studied by means of polarimetry. The effects exerted by the organic co-solvent on the conditional inclusion free energies Δ G cond 0 and the differential molar optical rotations Δ Θ were thoroughly analyzed under the perspective of the enthalpy–entropy compensation effect. Experimental data suggest an intimate participation (‘dynamic co-inclusion’) of solvent molecules in the formation and in the conformational dynamics of the host–guest inclusion complex.

First Evidence of Proline Acting as a Bifunctional Catalyst in the Baylis–Hillman Reaction Between Alkyl Vinyl Ketones and Aryl Aldehydes

Proline in the presence of sodium hydrogen carbonate has been found to be an effective catalyst for the Baylis–Hillman reaction between methyl or ethyl vinyl ketone and aryl aldehydes. Screening of several amine catalysts showed that an ionizable carboxylic function directly linked to the secondary amine catalyst plays an important role in the synthesis of the desired product in good yield. The data obtained has allowed us to suggest, for the first time, that proline, sarcosine, pipecolinic acid and homoproline may act as bifunctional catalysts via a bicyclic enaminolactone species as intermediate. Quantum-mechanical calculations (PM3/COSMO and ab initio 3-21G/COSMO) support this mechanism …

The binary pyrene/heptakis-(6-amino-6-deoxy)-β-cyclodextrin complex: A suitable chiral discriminator. Spectrofluorimetric study of the effect of some α-amino acids and esters on the stability of the binary complex

The effect of some α-amino acids and their esters on the stability of the binary pyrene/heptakis-(6-amino-6-deoxy)-β-cyclodextrin (py/am-β-CD) complex has been studied by means of fluorescence spectroscopy at two pH values (8.0 and 9.0). The binary complex was generally stabilized by adding the ternary agent at pH 8.0. A more varied substrate effect is observed at pH 9.0 where am-β-CD is present in the uncharged form. The conditional constant (β2) values determined by L/D α-amino acids show that the binary complex is a suitable receptor for chiral recognition. The enantiomer selectivity values obtained, ranging from 1.2 up to 7.4, are generally higher than those reported for α-amino acids a…

Supramolecular aggregation of bis-imidazolium functionalised perylene bisimides

Electronic and Steric Effects: How Do They Work in Ionic Liquids? The Case of Benzoic Acid Dissociation

The need to have a measure of the strength of some substituted benzoic acids in ionic liquid solution led us to use the protonation equilibrium of sodium p-nitrophenolate as a probe reaction, which was studied by means of spectrophotometric titration at 298 K. In order to evaluate the importance of electronic effect of the substituents present on the aromatic ring, both electron-withdrawing and -donor substituents were taken into account. Furthermore, to have a measure of the importance of the steric effect of the substituents both para- and ortho-substituted benzoic acids were analyzed. The probe reaction was studied in two ionic liquids differing for the ability of the cation to give hydr…

New simple hydrophobic proline derivatives as highly active and stereoselective catalysts for the direct asymmetric aldol reaction in aqueous medium

New 4-substituted acyloxyproline derivatives with different hydrophobic properties of the acyl group were easily synthesized and used as catalysts in the direct asymmetric aldol reaction between cyclic ketones (cyclohexanone and cyclopentanone) and several substituted benzaldehydes. Reactions were carried out using water, this being the best reaction medium examined. Screening of these catalysts showed that compounds bearing the most hydrophobic acyl chains [4-phenylbutanoate and 4-(pyren-1-yl)butanoate] provided better results. The latter catalysts were successfully used in only 2 mol% at room temperature without additives to give aldol products in excellent stereoselectivities. These resu…

One-pot synthesis of ZnO nanoparticles supported on halloysite nanotubes for catalytic applications

Abstract A versatile catalyst based on halloysite and zinc oxide (HNT@ZnO) was prepared, for the first time, starting from ZnO commercial bulk form as Zn precursor source, in a one-pot procedure. This strategy gives the possibility to obtain small ZnO nanoparticles loaded on the HNT surface without the use of inorganic salts which envisage the removal of undesired anions and therefore a calcination process at high temperature. It was found that the presence of halloysite improved the UV–vis spectral absorption ability of ZnO. The hybrid was successful used as photocatalyst for the methylorange and rhodamine B degradation. In addition, after eight consecutive cycles for the methylorange phot…

Substituent effects on the gas-phase basicities of4-x-acetophanes and 4-x-2,6-dimethylacetophenones: a comparison with solution basicities

Abstract The behaviour towards gas-phase protonation of a series of 2,6-dimethyl-4-X-acetophenones DM1 exhibits strong similarities with that of the corresponding 4-X-acetophenones 1 . A comparison with previous basicity data in solution and AM1 semiempirical calculations suggest that the X-dependent rotation of the probe group out of the plane of the aromatic ring caused by the two ortho methyls is of minor importance in influencing the substituent effect on the gas-phase basicity of DM1 ; on the contrary, it could heavily affect the solvatability and thus be responsible for the observed behaviour of DM1 in strongly acidic media.

Binding properties of heptakis-(2,6-di-O-methyl)-β-cyclodextrin and mono-(3,6-anhydro)-β-cyclodextrin: a polarimetric study

The binding constants for the inclusion complexes formed between heptakis-(2,6-di-O-methyl)-β-cyclodextrin (MβCD) and mono-(3,6-anhydro)-β-cyclodextrin (AβCD) with a set of suitably selected organic guests, were measured by means of polarimetry. Measurements were carried out at various pH values in order to ensure the correct protonation state for ionizable guests. Experimental data suggest that the binding properties of MβCD may be rationalized considering the less polar and more hydrophobic character of the cavity, although similar variations in conformational/dynamic behaviour occur as for native βCD. On the other hand, AβCD shows some similarities with αCD, due to the significant distor…

Stereoselective synthesis of substituted tetrahydropyran rings via 6-exo and 6-endo selenoetherification

Eight unsaturated alcohols were cyclized by selenoetherification in 6-exo or 6-endo manner to give substituted tetrahydropyran rings. Yields, regio- and stereoselectivities were discussed in terms of steric and electroniceffects such as Se-O interaction. For the first time examples of the use of silica gel in selenoetherification and the effect of the X - counter ion of PhSe + on the reaction course are discussed. These effects are related to the occurrence of Se-O interaction.

Effetto del cosolvente sulla velocità della reazione di trasposizione eterociclica mononucleare della Z-fenilidrazone del 3-benzoil-5-fenil-1,2,4-ossadiazolo in liquido ionico

Binding porperties of hetpakis-(2,6-di-O-methyl)-beta-cyclodextrin and mono-(3,6-anydro)-beta-cyclodextrin

Toward More Efficient Organocatalysts

Thermodynamics of binding between α- and β-cyclodextrins and some p-nitro-aniline derivatives: reconsidering the enthalpy–entropy compensation effect

Abstract The thermodynamics of binding between native α- and β-cyclodextrin towards several p -nitro-aniline derivatives was examined, in order to gain further insights about the occurrence of different interaction modes for the two hosts. Valuable information was achieved regarding the ‘expanded hydrophobic sphere’ of α-cyclodextrin. Furthermore, very interesting and unexpected aspects of the behavior of β-cyclodextrin were enlightened, such as the crucial role played by hydrogen bond interactions. Experimental data were examined under the perspective of the ‘enthalpy–entropy compensation effect’, and some ideas about this topic are discussed.

Cyclodextrin–calixarene co-polymers as a new class of nanosponges

Hyper-reticulated co-polymers jointly formed by cyclodextrin and calixarene units, which can be considered as a new class of nanosponges, were easily obtained by means of a click chemistry approach. In particular, we succeeded in preparing our materials by exploiting the copper-catalyzed 1,3-dipolar cycloaddition (CuAAC) reaction between heptakis-(6-deoxy)-(6-azido)-beta-cyclodextrin and (5,11,17,23-tetra-tert-butyl)-(25,26,27,28-tetra-propargyloxy)-calix-[4]-arene, mixed in different proportions. These materials were fully characterized by means of combined FT-IR, thermogravimetric, C-13 {H-1} CP-MAS NMR and nitrogen adsorption/desorption techniques. In particular, C-13 {H-1} CP-MAS spectr…

Eco-friendly functionalization of natural halloysite clay nanotube with ionic liquids by microwave irradiation for Suzuki coupling reaction

Abstract Microwave assisted halloysite (HNT) external surface functionalization with ionic liquids is described. HNTs modification was achieved in two steps: a) grafting of 3-mercaptopropyl trimethoxysilane on the external surface of HNT by a microwave irradiation; b) anchorage of vinylimidazolium ionic liquids by a thiol-ene reaction. MW irradiation allowed us to obtain high loading onto the HNT surface compared to those obtained through conventional synthesis. Fourier transform infrared spectroscopy and thermogravimetric analysis confirmed that the grafting has occurred only on the external surface of HNT. Turbidimetric and dynamic light scattering analyses showed that the introduction of…

Polystyrene supported L-proline: a recyclable organocatalyst for the asymmetric aldol reaction in the presence of water

Functionalized Diatonic Ionic Liquids Applied to the Study of Michael Addition

Novel supported substituted prolinamide as recyclable catalyst for asymmetric aldol reaction

Spectrophotometric study on the thermodynamics of binding of α- and β-cyclodextrin towards some p-nitrobenzene derivativesElectronic supplementary information (ESI) available: Values of inclusion constants at different temperatures. See http://www.rsc.org/suppdata/ob/b3/b300330b/

Binding properties of native α- and β-cyclodextrin towards some nitrobenzene derivatives have been studied by means of UV-vis spectrophotometry. The former host is able to form complexes having 1 : 1 and 1 : 2 stoichiometric ratios with these guests, while only 1 : 1 complexes are detected with the latter host. A careful analysis of the thermodynamic parameters for complexation equilibria, under the perspective of the enthalpy–entropy compensation effect, reveals that binding abilities of the two different hosts are subject to different features.

CHEMICAL MODIFICATIONS OF HALLOYSITE NANOTUBES FOR THE DEVELOPMENT OF SMART NANOMATERIALS

Halloysite nanoclays (HNTs) are promising nanomaterials because of their versatile properties, such as hollow tubular morphology and tunable surface chemistry. HNTs are biocompatible, no toxic and abundantly available at low cost. Due to these characteristics HNTs are suitable for development of hybrid sustainable materials, which are perspective for wastewater remediation, green packaging and drug delivery. HNTs are quite polydisperse in size with a length of ca. 1 m, while the external diameter and the lumen range between 50-80 nm and 10-15 nm, respectively. Chemically, halloysite is composed of gibbsite octahedral sheet (Al-OH) groups on the inner surface and siloxane (Si−O−Si) groups o…

Di- and Tricationic Organic Salts: An Overview of Their Properties and Applications

During recent years growing interest has been devoted to the synthesis and applications of polycationic organic salts. Among them, di- and tricationic organic salts can be considered the natural evolution of monocationic ones. These last have given rise to the large class of ionic liquids. In the cases of di- and tricationic organic salts, the potential to change their structural features simply by varying the properties either of the charged heads or of the spacers separating them provides the opportunity to obtain materials suitable for different applications. This review article highlights recent progress in the study of the properties of di- and tricationic organic salts, as well as in …

New ionic liquid-modified silica gels as recyclable materials for L-proline- or H-Pro-Pro-Asp-NH2-catalyzed aldol reaction

l-proline and the tripeptide H-Pro-Pro-Asp-NH2 (1) have been supported, by adsorption, onto the surface of modified silica gels functionalized with a monolayer of covalently attached 1,2-dimethyl-imidazolium chloride, tetrafluoroborate or hexafluorophosphate ionic moieties, respectively. Three different linkers were used to attach the ionic liquid moiety to the surface of these supports. The resulting materials have been used as catalysts for the aldol reaction between acetone and several substituted benzaldehydes. Good yields and enantioselectivities, comparable to or better than those obtained under homogeneous conditions, were obtained. These materials are easily recovered by filtration,…

CONVERSIONE CHEMO-ENZIMATICA DI GLUCOSIO IN 5-HMF IN MISCELE IL/H2O, PROMOSSA DA ESTRATTO CELLULARE BATTERICO E ULTRASUONI

From covalently linked catalysts to "release and catch" catalytic systems

Di- and Tricationic Organic Salts: an Overview of Their Properties and Applications

During recent years growing interest has been devoted to the synthesis and applications of polycationic organic salts. Among them, di- and tricationic organic salts can be considered the natural evolution of monocationic ones. These last have given rise to the large class of ionic liquids. In the cases of di- and tricationic organic salts, the potential to change their structural features simply by varying the properties either of the charged heads or of the spacers separating them provides the opportunity to obtain materials suitable for different applications. This review article highlights recent progress in the study of the properties of di- and tricationic organic salts, as well as in …

Advantages in supporting chiral organocatalysts

An overview on the advances in supporting organocatalysts for their use and recycle in the asymmetric synthesis is presented, focusing on the main approaches for the immobilization and highlighting those examples in which supported and unsupported version of the catalyst behave similarly and high level of recyclability have been obtained.

Nanoparticelle di Ag-poliamminoCD come catalizzatori per la riduzione di nitrocomposti aromatici

Sistemi nanoparticellari di Argento protetti con poliammino-beta-ciclodestrine sono stati preparati, caratterizzati, e impiegati come catalizzatori per la riduzione con boroidruro di sodio di una serie di nitrocomposti aromatici modello 1-8. Tale reazione costituisce una interessante alternativa rispetto ai metodi di riduzione più comuni (LiAlH4, Zn/HCl), che prevedono l’uso di condizioni di reazione piuttosto drastiche. La cinetica della reazione considerata è stata approfonditamente studiata al fine di chiarire il ruolo meccanicistico del catalizzatore. E’ stato trovato, infatti, che il processo risulta di ordine misto rispetto al substrato, e che le costanti cinetiche apparenti di reazio…

Hydrophobically Directed Aldol Reactions: Polystyrene-SupportedL-Proline as a Recyclable Catalyst for Direct Asymmetric Aldol Reactions in the Presence of Water (Eur. J. Org. Chem. 28/2007)

The cover picture shows the aldol reaction between ketones and arylaldehydes carried out by using a polystyrene-supported L-proline catalyst. This material furnishes aldol products in high yields and stereoselectivities. Screening of solvents showed that these reactions take place only in the presence of water. This solvent effect, coupled with the high stereoselectivities observed, has been explained by the formation of a hydrophobic core in the inner surface of the resin with the hydrophilic proline moiety in the resin/water interface. Such a microenvironment promotes the aldol reaction and increases the stereoselectivity. Recycling investigations have shown that this material can be reus…

“Release and catch” catalytic systems

In this perspective article the “release and catch” catalytic system concept is discussed. A “release and catch” catalytic system is prepared by non-covalent immobilization of the catalytic moiety on a suitable support, but differently from the usual non-covalently supported catalyst, the catalytic moiety is released in solution over the course of the reaction and it is recaptured at the end of the reaction. Such a “catalyst- sponge like” or “boomerang” system allows one to combine the benefits of homogeneous and heterogeneous catalysis and can be applied to organometallic-based catalysts, organocatalysts and metal-based catalysts.

L-Prolina supportata su polistirene come catalizzatore eterogeneo nella reazione di condensazione aldolica “in the presence of water”