Synthesis and characterization of tetrakis‐ derivatives of bisphenol‐A with 4‐phenylazoaniline and 5‐(4‐aminophenylazo)‐25,26,27‐tribenzoyloxy‐ 28‐hydroxycalix[4]arene

The synthesis of tetrakis‐ derivatives of bisphenol‐A containing azo groups at their 2,2′,6,6′‐positions is reported. Novel examples of bisphenol‐A, coupled with diazonium salts and derived from 4‐phenylazoaniline and 5‐(4‐aminophenylazo)‐25,26,27‐tribenzoyloxy‐28‐hydroxycalix [4]arene, have been synthesized. It has been observed that the coupling reaction of diazonium salt obtained from 4‐phenylazoaniline with bisphenol‐A gives tetrakis‐ while those derived from 5‐(4‐aminophenylazo)‐25,26,27‐tribenzoyloxy‐28‐hydroxycalix [4]arene give partially substituted bisphenol‐A analogues. The newly prepared tetrakis‐azo substituted bisphenol‐A compounds ( 1 and 2 ) are characterized by using UV‐vis, FT‐IR, ¹H‐NMR spectroscopic methods as well as elemental analysis techniques. These azo compounds give rise to bathochromic shifts in the absorption spectra, which can even be detected by “naked eye.” © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Characterization of polypyrrole/azocalix[4]arene salts: Electrical properties and thermal stability

Polypyrrole (PPy) was doped with the azocalix[4]arene [(5,11,17,23‐tetrakis[(p‐carboxyphenyl)azo]25,26,27,28‐tetrahydroxycalix[4]arene)] host species. PPy/azocalix[4]arene salts were characterized by FTIR, TGA, SEM, X‐ray diffraction, and conductivity measurements. The properties of PPy were investigated in the presence of azocalix[4]arene host species. The conductivity of PPy increased in the presence of azocalix[4]arene. TGA results indicated that the PPy/azocalix[4]arene salts have higher thermal stability than PPy. It was observed from SEM analysis that the particle diameter of PPy decreased with increasing content of azocalix[4]arene. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Calix[4]arene‐tetranitrone as crosslinker in dental composite materials

The synthesis of a functionalized calix[4]arene bearing 1,3‐dipolaric nitrone groups ( 5 ) has been carried out. The reaction of N‐methylhydroxylamine or N‐propylhydroxylamine with the carbonyl group of 5,11,7,23‐tetraformyl‐25,26,27,28‐tetraalkoxycalix[4]arene leads to calix[4]arenes bearing a nitrone function at each of the four para‐positions. Via 1,3‐dipolar cyclo‐addition of acrylic acid methyl ester with the nitrone functions of 5 , subsequently an upper rim‐substituted tetraisoxalidinecalix[4]arene is quantitatively synthesized. Further, the minimization of shrinkage of a dental filling depending on the amount of calix[4]arene‐tetranitrone is discussed. Copyright © 2011 Society of Chemical Industry     

Synthesis and characterization of calix[4]arene‐containing polyimides

Three types of amino‐functionalized calixarenes, i.e. the diaminocalix[4]arenes 5,17‐diaminomethyl‐25,26,27,28‐tetrapropoxycalix[4]arene, 25,27‐diaminoethoxy‐26,28‐dihydroxycalix[4]arene and 5,11,17,23‐tetra‐tert‐butyl‐25,27‐diaminoethoxy‐26,28‐dihydroxycalix[4]arene, were synthesized and incorporated as comonomers into the backbones of aromatic polyimides. As a first step, polyimide precursors (poly(amic acid)s) were prepared by condensation reaction of diamine with dianhydride at the stoichiometric ratio. The diamine component was composed of synthesized diaminocalix[4]arene and commercial 4,4′‐oxydianiline combined in various molar ratios. The dianhydride used was 4,4′‐oxydiphthalic anhydride. The poly(amic acid)s were characterized using intrinsic viscosity measurements and their chemical composition was determined using ¹H NMR spectroscopy. The precursors were then transformed into the polyimides using a thermal treatment. Thermal and dynamic mechanical behaviour, wide‐angle X‐ray diffraction and solubility of the resulting polyimide films in selected solvents were evaluated. The structure–property relationship of the novel types of synthesized polyimides is discussed in terms of the calixarene monomer used and the fraction of it incorporated into the polymer backbone. Copyright © 2010 Society of Chemical Industry     

A useful approach toward the synthesis and metal extractions with polymer appended thioalkyl calix[4]arenes

This article describes a convenient method for the synthesis of two new polymeric resins via nucleophilic substitution reactions involving 5,11,17,23-tetrakis[(propylthio)methyl]-25,26,27,28-tetrahydroxycalix[4]arene 4, and 5,11,17,23-tetrakis[(methylthio)methyl]-25,26,27,28-tetrahydroxycalix[4]arene 6, as precursors with Merrifield's resin. The extraction studies were made using both liquid-liquid extraction and solid-liquid batchwise sorption procedures. The calix[4]arene based polymeric resins have high extraction ability toward metal cations and Na₂Cr₂O₇ as compared to their monomeric precursors.     

Molecular Reinforcement of Transparent Materials With Acrylamide‐Modified Calix[4]arene as a Crosslinker

The synthesis of 5,11,17,23‐amino‐25,26,27,28‐propoxycalix[4]arene (calix[4]amine, 4 ) starting from 5,11,17,23‐nitro‐25,26,27,28‐propoxy‐calix[4]arene ( 3 ) via microwave‐assisted transfer hydrogenation is reported. Furthermore, the calix[4]amine ( 4 ) is functionalized with an acrylamide moiety. The swelling behavior in water, the influence on the glass transition temperature, and the shear modulus of a crosslinked N,N‐dimethylacrylamide (NDA) polymer with 5,11,17,23‐acrylamido‐25,26,27,28‐propoxycalix[4]arene ( 5 ) and EGDMA, respectively, are investigated.

     

Dechema corrosion handbook Vol. 3 Edited by D. Behrens,VCH Verlagsgesellschaft,Weinheim Frankfurt am Main, 1988. pp. ix + 282, price £286.00 (subscription price to series £238.00 per volume) ISBN 3-527-26654-2

4-Phenyl-5-aminopyrazole 2 obtained from phenylcyanoacetaldehyde 1 and hydrazine hydrate reacted with diethyl malonate to give 3-phenyl-5,7-dioxopyrazolo[1,5-a]pyrimidine 3 , used as the key compound in the synthesis of arylazo dyes. The key compound 3 was coupled with various aryldiazonium salts 4 to yield 3-phenyl-7-hydroxy-6-arylazopyrazolo[1,5-a]pyrimid-5-ones 5. The resulting arylazo dyes (5) were refluxed in phosphorus oxychloride to give 3-phenyl-5,7-dichloro-6-arylazo-pyrazolo[1,5-a]pyrimidines 6 , which subsequently reacted with refluxing morpholine and piperidine to yield 3-phenyl-5,7-bis(morpholino and piperidino)-6-aryiazopyrazolo[1,5-a]pyrimidines 7. The arylazo dyes 5 and 7 were applied to polyester fibres as disperse dyes and the arylazo dyes 6 were applied to polyamide fibres as disperse reactive dyes. The spectral and dyeing properties of the dyes were studied.     

Novel anti‐bacterial acid dyes derived from naphthalimide: synthesis,characterisation and evaluation of their technical properties on nylon 6

As an attempt to combine the dyeing and functional finishing steps into one process, two novel anti‐bacterial monoazo acid dyes based on N‐ester‐1,8‐naphthalimide were synthesised. To do this, 4‐amino‐N‐ethyl glycinate‐1,8‐naphthalimide was prepared, diazotised and then coupled to thiosalicylic acid or salicylic acid to produce anti‐bacterial dyes. The synthesised dyes were purified and then fully characterised using Fourier Transform–infrared spectrometry, proton nuclear magnetic resonance spectroscopy and melting point analysis. Dispersion of the dyes was prepared in water and applied to nylon 6 fabrics. The novel dyes offered good build‐up properties on the substrate. The anti‐bacterial efficacy of the synthesised dyes was assessed, with the dyes showing activity against both Gram‐positive and Gram‐negative bacteria.     

Synthesis and binding properties of polymeric calix[4]arene nitriles

Two new polymers containing pendant calix[4]arene units with nitrile functionalities at their lower rim have been synthesized via radical initiated reactions involving a vinylic monomer 6 {5,11,17,23-tetra-tert-butyl-25,26,27-tris(cyanomethoxy)-28-(2-acryloyloxy) ethoxycalix[4]arene} and with styrene. A five atom spacer group was incorporated between the bulky calixarene core and the acrylate moiety in order to minimize steric interactions which proved to impede the polymerization. The complexation studies were made by using liquid–liquid extraction procedures. It has been deduced from the observations that both polymers show a good selectivity towards Hg²⁺ like their precursor 5,11,17,23-tetra-tert-butyl-25,26,27-tricyanomethoxy-28-(2-hydroxy)ethoxycalix[4]arene 5, which supports their utility as adsorbents or potential candidate materials for fabricating membranes and sensors, which can separate or detect Hg²⁺ metal ions in a high selectivity.     

mPW1PW91 study for conformational isomers of methylene bridge-monosubstituted tetramethoxycalix[4]arenes

Structures of ten conformational isomers of methylene bridge-monosubstituted tetramethoxycalix[4]arenes, 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetramethoxy-2-ethylcalix[4]arene (1), and methyl 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetramethoxycalix[4]arene-2-carboxylate (2) were optimized by quantum mechanical mPW1PW91/6-31G(d,p) (hybrid Hartree–Fock density functional) calculations. The total electronic and Gibbs free energies of the various conformations (cone, partial cone, 1,2-alternate, and 1,3-alternate) of 1 and 2 were analyzed. The cone (equatorial) and partial cone (equatorial) conformers were disclosed to be the most stable among all the isomers of 1 and 2. The calculated structures agreed well with the experimental results. The IR spectra were calculated at the mPW1PW91/6-31G(d,p) level for the most stable conformer of each methylene bridge-monosubstituted tetramethoxycalix[4]arene.     

Methacrylated calix[4]arene phosphonic acids as functionalized crosslinker for radical polymerization

We describe the synthesis of 5,11,17,23‐tetra‐tert‐butyl‐25,27‐dioxypropylphosphonic acid‐26,28‐dimethacryloyloxy‐calix [4]arene and 5,11,17,23‐tetra‐tert‐butyl‐25‐oxypropylphosphonic acid‐27‐hydroxy‐26,28‐dimethacryloyloxy‐calix[4]arene starting from para‐tert‐butyl‐calix[4]arene. The complete reaction was proved by matrix‐assisted laser desorption ionization time of flight mass spectrometry and nuclear magnetic resonance spectroscopy. The influence of these compounds on the kinetics of the radical polymerization of methyl methacrylate was shown by dilatometry. Furthermore, the adhesive properties of dental adhesives containing these calix[4]arene derivatives were investigated. Copyright © 2012 Society of Chemical Industry     

Synthesis of novel 3‐hetaryl‐substituted 6‐ and 8‐hydroxybenzo[f]coumarin derivatives

Eight novel 3‐hetaryl‐substituted 6‐ and 8‐hydroxybenzo[f]iminocoumarin compounds were synthesised by the reaction of 2,5‐dihydroxynaphthaldehydes or 2,7‐dihydroxynaphthaldehydes with 2‐cyanomethylbenzo‐thiazole, 2‐cyanomethylbenzoimidazole, 1‐methyl‐2‐cyanomethylbenzoimidazole and 2‐cyanomethyl‐4‐phenylthiazole. The iminocompounds obtained were hydrolysed with hydrochloric acid to the benzo[f]coumarins. Becaue of the high reactivity of the iminocoumarins, only mixtures which also contained the corresponding coumarin compounds were isolated. The absorption and steady‐state fluorescence characteristics of the benzo[f]coumarins (benzo[f]chromen‐2‐ones) synthesised were studied in ethanol and in toluene.     

Liquid Membrane Transport of Hg(II) by an Azocalix[4]arene Derivative

Abstract

A kinetic study of Hg(II) transport from an aqueous donor solution into an aqueous acceptor solution through a liquid membrane containing 25,26,27–tribenzoyloxy‐28‐hydroxy‐5,11,17,23‐tetra‐(4‐n‐butylphenylazo)calix[4]arene 1 as a carrier was studied. The kinetic parameters (k ₁, k ₂, R _m ^max, t _max, J _d ^max, J _a ^max) for the transport were investigated in terms of the effect of temperature, the stirring rate, the carrier concentration, and the type of solvent. The kinetics of transport was analyzed in the formalism of two consecutive irreversible first‐order reactions. The membrane entrance rate, and exit rate constants were increased with increasing of temperature stirring rate, and carrier concentration. The membrane entrance rate and exit rate constants depended on the type of solvent and was found to be in order of CH₂Cl₂> CHCl₃> CCl₄. The activation energy values are calculated as 30.67±2.64 and 57.33±4.90 kj mol^?1 for extraction and reextraction, respectively. The values of calculated activation energy indicate that the process is diffusionally controlled by species.     

Synthesis and application of some novel antimicrobial monoazonaphthalimide dyes: synthesis and characterisation

A series of novel monoazo dyes based on N‐pyridine‐1,8‐naphthalimides were prepared using 4‐amino‐N‐2‐aminomethylpyridine‐1,8‐naphthalimide as the diazo component and N,N‐diethyl‐meta‐toluidine, 3‐(N,N‐diethylamino)acetanilide and N‐hydroxyethyl‐N‐ethylaniline as the coupling components. The synthesised dyes were purified by utilising column and preparative thin‐layer chromatography methods. The characterisations of the prepared dyes were carried out by differential scanning calorimetery, thin‐layer chromatography (R_f values), Fourier Transform infrared, and proton and carbon nuclear magnetic resonance techniques. The in vitro antibacterial activity of the novel synthesised compounds against Escherichia coli, Staphylococcus aureus, Bacillus subtilis and their antifungal activity against Candida albicans were evaluated by use of conventional agar dilution procedures and a minimum inhibitory concentration. Some of these synthesised dyes demonstrated antibacterial activity against Gram‐positive bacteria in addition to antifungal activities.     

Antimicrobial activity of some new 4‐arylazo‐3‐methylthiophene disperse dyes on polyester fabrics

A series of novel 4‐arylazo‐3‐methylthiophenes was synthesized by the heterocyclization of 2‐arylhydrazono‐2‐acetyl thioacetanilide derivatives with a variety of α‐halogenated reagents, such as chloroacetone, phenacyl bromide, ethyl chloroacetate, and chloroacetonitrile. The structures of the synthesized thiophene derivatives were confirmed by ultraviolet–visible, IR, and ¹H‐NMR spectroscopic techniques and elemental analysis. The synthesized dyes were applied to polyester fabrics as disperse dyes, and their fastness properties were evaluated. The dyed polyester fabrics displayed antibacterial efficacy against Gram‐positive (Staphylococcus aureus) and Gram‐negative (Escherichia coli) bacteria. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Dyes derived from 3‐formyl‐2(1H)‐quinolone – synthesis,spectroscopic characterisation,and their behaviour in the presence of sulfhydryl and non‐sulfhydryl amino acids

Novel dyes based on a 3‐formyl‐2(1H)‐quinolone skeleton were synthesised and characterised using ¹H nuclear magnetic resonance spectroscopy and mass spectrometry. The spectroscopic properties of these dyes, such as their absorption spectra, emission spectra, and quantum fluorescence yields, were also examined. The behaviour of the obtained compounds at a pH of 7.4 in the absence and in the presence of thiol amino acids, such as l ‐cysteine, l ‐glutathione, and N‐acetyl‐l ‐cysteine, were studied. The spectroscopic responses of the tested dyes towards other amino acids were also investigated. A reference compound was synthesised to understand the reaction mechanism between the thiols and the obtained dyes. The experimental results show that the synthesised dyes have the potential to act as sensors for thiols.     

The removal of Cr(VI) through polymeric supported liquid membrane by using calix[4]arene as a carrier

In this work, the transport and removal of Cr(VI) were achieved through supported liquid membrane (SLM) by using a 5,17, di-tert-butyl-11,23-bis[(1,4-dioxa-8-azaspiro [4,5]decanyl)methyl]-25,26,27,28-tetrahydroxy calix[4]arene carrier, dissolved in 2-nitrophenyl octyl ether dichloromethane. The studied parameters are the solvent effect in the membrane phase, the effect of carrier concentration, and the acid type in the donor phase. The Celgard 2500 was used as a membrane support. We used the Danesi mass transfer model to calculate the permeability coefficients for each studied parameter. In addition, AFM and SEM techniques were used to characterize the surface morphology of the prepared Celgard 2500 membrane that included the calix[4]arene carrier.     

Thermal Behaviors of Bisazocalix[4]arene Derivatives

In this article, calix[4]arene (4) was prepared by debutylation and hydrolyses reacting from 25,27-dibenzoyl-26,28-dihydroxy-5,11,17,23-tetra(tert-butyl)calix[4]arene (2). Azocalix[4]arenes (6a-c) were coupled by linking 4-methoxy, 4-ethyl, and 4-nitroaniline to calix[4]arene (4) through a diazo-coupling reaction. Thermal behavior characteristics and decomposition routes of 25,26,27,28-tetrahydroxy-11,23-di(tert-butyl)-5,17-(p-substitue phenyl)azocalix[4]arene (6a-c) were investigated in air atmosphere by means of thermogravimetry (TG), differential thermogravimetry (DTG), and differential thermal analysis (DTA) analyses. It was found that the decomposition of all compounds complete with two exothermic stages which corresponded to removal of substitute groups (methoxy-, ethyl-, nitro-) and second stage rest of structure decomposition.     

Synthesis and colour spectroscopic investigation of some hemicyanine dyes

New hemicyanine dyes with a benzo[2,3‐b;2′,3′‐b′]bis‐furo[3,2‐d]pyrazolium nucleus were prepared. Spectroscopic investigations were carried out in 95% ethanol for all the synthesised cyanine dyes and/or in pure solvents which have different polarities for some selected dyes. Structural identification was carried out via elemental analysis, infra‐red and proton nuclear magnetic resonance spectral data.     

Blue solid‐state luminescent tetraphenylethene–organophosphorus dyads with aggregation‐induced emission characteristics

Three novel tetraphenylethene–organophosphorus dyads – (6‐oxido‐6H‐dibenz[c,e][1,2]oxaphosphorin‐6‐yl)[4‐(1,2,2‐triphenylvinyl)phenyl] methanol, diphenyl {hydroxy[4‐(1,2,2‐triphenylvinyl)phenyl]methyl} phosphine oxide, and di(3,5‐dimethylphenyl){hydroxy[4‐(1,2,2‐triphenylvinyl)phenyl] methyl} phosphine oxide – were synthesised and characterised by ¹H, ¹³C, and ³¹P nuclear magnetic resonance spectroscopy, mass spectrometry, and elemental analysis. The photoluminescence properties were studied. All three dyads exhibited intense solid‐state blue emission peaking at 449–466 nm, and also displayed aggregation‐induced emission behaviours. The emission decays of these dyads in the solid state also fitted well with a triexponential model with an average lifetime of 2.65–4.42 ns. The experimental results demonstrated that the luminescent properties are highly dependent on the nature of the organophosphorus groups. The choice of phosphorus‐containing components can cause variations in the photoluminescence emission and photoluminescence decays.