Friedel-Crafts Polymers. 6. Friedel-Crafts Polycondensation of p-Xylylerte Dibromide with Salicylic Acid and β-Resorcyiic Acid

Polymers were prepared by condensing p-xylylene dibromide separately with salicylic acid and β-resorcylic acid in the presence of anhydrous ferric chloride in dioxane. The polymer samples_were characterized by elemental analysis, by IR spectral study, by M determined by vapor pressure osmometry, by nonaqueous conducto-metric titration in pyridine, by TGA in air, and by viscosity measurements of polymer solutions in DMF. Polymeric metal chelates of Cu²⁺, Co²⁺, Zn²⁺, Ni²⁺, and Fe³⁺ with polymer samples were prepared and characterized by elemental analysis, by IR spectral study, and by TGA in air. The chelation ion-exchange properties of the polymer samples were studied by employing the batch equilibration method.     

Synthesis and characterization of 2, 4-dihydroxy-benzaldehydeoxime-formaldehyde polymers and their application as ion-exchangers

Polymers were prepared by the condensation of 2, 4-dihydroxybenzaldehydeoxime (2, 4-DBO) and formaldehyde (F) in the presence of oxalic acid as catalyst with varying molar ratios of reacting monomers. Polymers were characterized by their IR spectra, elemental analyses, TGA and M_n as determined by vapour pressure osmometry as well as by non-aqueous conductometric titrations. Viscosity measurements of the solutions of polymer samples were carried out in dimethylformamide. Chelation ion-exchange properties have also been studied employing the batch equilibration method. This method involved the measurement of distribution of a given metal between the polymer sample and a solution containing metal ions. The study was carried out over a wide pH range and in media of various ionic strengths. The polymer showed a higher selectivity for UO ₂ ²⁺ and Fe³⁺ ions than for Cu²⁺, Ni²⁺, Co²⁺ and Mn²⁺ ions.     

Resacetophenone-furfural polymers

Poly(resacetophenone-furfural) was prepared by condensing resacetophenone with furfural in the presence of the optimum concentrations of various acidic catalysts. The polymer samples were characterized by elemental analyses, i.r. spectra and TGA. The number-average molecular weights were determined both by vapour pressure osmometry and non-aqueous titration. Intrinsic viscosities of the polymers were measured in DMF. Polymeric metal chelates of Cu²⁺, Fe³⁺, Co²⁺, Zn²⁺, Mn²⁺, Ni²⁺ were prepared and characterized.     

Co-ordination polymers of bis(8-hydroxy-5-quinolylmethylene) sulphide (BHQS)

Co-ordination polymers of bis(8-hydroxy-5-quinolylmethylene)sulphide have been prepared with Zn²⁺, Cu²⁺, Ni²⁺, Co²⁺ and Mn²⁺ ions and characterized by elemental analyses, by i.r. and diffuse reflectance spectral studies and by magnetic moment. The metal contents in all polymers are found to be consistent with 1:1 (metal:ligand) stoichiometry. The thermal behaviour of each of the co-ordination polymer has been studied by TGA in air up to 700°C.     

Synthesis, characterization and chelating properties of poly [azo-(6-hydroxy-1,3-phenylene)]

Poly [azo(6-hydroxy-1,3-phenylene)] (PAHP) was prepared by alcoholic alkaline reduction of 2,4-dinitro phenol (DNP). The polymers prepared at various time intervals were characterized by elemental analyses, IR spectra and thermogravimetric analysis. The number average molecular weight was determined by non-aqueous titration. Viscometric study in DMF of all the three polymers were carried out and indicates polyelectrolyte behaviour. Viscometric study in DMF-water (85:15)(v/v) containing 1%KBr shows normal behaviour. Polymeric metal chelates of Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺, Mn²⁺ and Cr²⁺ with PAHP polymer were prepared and characterized.     

PAS-Formaldehyde Polymer as a Polymeric Ligand

p-Aminosalicylic acid (PAS) was condensed with formaldehyde in the presence of aqueous oxalic acid and aqueous sodium hydroxide. The polymer sample (PAS-F,1) obtained withacid catalyst was characterized by IR spectral study, by its M_n determined by nonaqueous conductometric titration both against standard acid and alkali, by viscometric study in formic acid, and by DTA. The IR spectral and general characteristics of a polymer sample (PAS-F,2) prepared in the presence of aqueous alkali resemble those of a polymer sample (AP-F) prepared similarly from m-aminophenol and formaldehyde, indicating decarboxylation of PAS during the base-catalyzed polymerization of PAS with formaldehyde. Polymeric metal chelates of Fe(III), Cu(II), Zn(II), and Mn(II) ions with the PAS-F,1 polymer sample have been prepared and characterized by elemental analyses, IR spectral study, measurements of magnetic moments, and thermal analyses. Chelation ion-exchanging properties of the PAS-F,1 polymer sample have also been studied employing the batch equilibration method.     

Synthesis and reactivity of metal-containing monomers 49. Synthesis and structure of low-valence transition metal acrylates and their polymers

The methods for synthesis of Cu¹⁺, Fe²⁺, Cr²⁺, and V³⁺ acrylates were elaborated. The compounds obtained were characterized by elemental analyses, data of IR, X-ray photoelectron, and Mössbauer spectroscopy, magnetochemistry, and mass spectrometry. Polymeric products were obtained by liquid-phase radical polymerization of metal acrylates. Changes in the electronic state of the ions and their nearest ligand environment during polymerization were observed.     

Fluorescence sensors for Cu2+ based on conjugated indole Schiff base

Two new conjugated Schiff bases were prepared by condensation reactions between indole derivatives and o-phenylenediamine, respectively. The structures of the synthetic compounds were characterized by IR, ¹H NMR, and elemental analysis. And the melting point determination revealed that both compounds have good thermal stability. Their fluorescence measurements indicated that both compounds in solution have excellent performance on fluorescence emission, and the intensity of fluorescence emissions was quenched sharply by adding copper (II) nitrate. And the spectral changes were examined upon addition of various metal ions, such as Cu²⁺, Cd²⁺, Co²⁺, Ni²⁺, and Zn²⁺. The results indicated that the fluorescence intensity of two compounds quenched dramatically, and the quenching efficiency of Cu²⁺ was the highest.     

Preparation and characterization of cellulose acetate complexes

Summary Metal chelates of secondary cellulose acetate (SCA) with chromium(III), copper(II), cobalt(II), nickel(II) and UO ₂ ²⁺ were prepared and characterized by elemental analyses, magnetic moments and spectral studies. SCA acts as a uninegatively charged bidentate ligand and reacts with the metal ion via the oxygen atom of the secondary unacetylated hydroxyl group in the glucose subunit of the polymer, plus the oxygen atom of the vicinal ester group, to form a five-membered chelate ring.     

Synthesis of iminooxime derivatives and investigation of their complexes

Three novel ligands, a-pycolyliminoisonitrosoacetophenone (L¹H · HCl), α-pycolylimino-p-methylisonitrosoacetophenone (L²H · HCl), and a-pycolylimino-p-chloroisonitrosoacetophenone L³H, were synthesized. Their metal complexes with Co(II), Cu(II), and Ni(II) were prepared. The mononuclear complexes of these ligands with Co²⁺, Cu²⁺, and Ni²⁺ ions were obtained in ethanol. The structures of the ligands and their complexes were characterized by 1H NMR, IR spectroscopy, elemental analyses, and magnetic susceptibility. The text was submitted by the authrs in English.     

Synthesis and magnetic properties of novel polymeric complexes containing bithiazole rings

A novel linear polymer (PFABT) containing bithiazole rings was synthesized by polycondensation of 2,2′‐diamino‐4,4′‐bithiazole (DABT) and formaldehyde. The complexes of PFABT with two transition metal ions (Fe²⁺, Cu²⁺) were prepared for the first time. The polymer was determined through FT‐IR, ¹H‐NMR and elemental analysis (EA), and the complexes were characterized by FT‐IR. The magnetic behaviors of these complexes were measured as a function of magnetic field strength (0–50 kOe) at 4 K and as a function of temperature (4–300 K) under an applied magnetic field of 30 kOe. The results show that PFABT‐Cu²⁺ is a ferromagnet while PFABT‐Fe²⁺ is an anti‐ferromagnet. Copyright © 2007 John Wiley & Sons, Ltd.     

A new chelating resin containing 2-aminothiophenol: Synthesis characterization and determination of mercury in waste water using <Superscript>203</Superscript>Hg radiotracer

A new stable chelating resin was synthesized by incorporating 2-aminothiophenol into Merrifield polymer through C-N covalent bond and characterized by elemental analysis, IR and thermal study. The sorption capacity of the newly formed resin for Hg²⁺ as a function of pH has been studied using ²⁰³Hg radioisotope. The resin exhibits no affinity to alkali or alkaline earth metal ions and common anions. The separation of mercury(II) in presence of different alkali and alkaline earth metal ions (Na⁺, K⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺), common anions (ClO₄ ⁻, SO₄ ²⁻) and other diverse ions (Ag⁺, Cu²⁺, Pb²⁺, Fe³⁺, Ni²⁺ and Zn²⁺) has been checked. In column operation it has been observed that Hg²⁺ content of the waste water can be removed at usual pH of natural water. Mercury was determined by isotope dilution method and the concentration of Hg²⁺ in the waste water spiked with ²⁰³Hg was found to be 0.05 to 0.09 μg/ml.     

Mononuclear and homobinuclear vanadium(IV), chromium(III), molybdenum(III), and uranium(VI) chelates with ortho-cresolphthalein complexone

Mononuclear and homobinuclear o-cresolphthalein complexone complexes with VO²⁺, Cr³⁺, MoO⁺, and UO₂ ²⁺ have been prepared and their structures investigated. The empirical formulas, the mode of bonding, and the geometry of the complexes were obtained from elemental and thermal analyses, IR, electronic and ESR spectra, magnetic moment determinations, DC and CV polarographic studies.     

Solvent Extraction of Heavy Metals with a 23-Membered Macrocyclic Ionophore Attached with BF 2 + -Capped Cobalt(III) Complex

A new (E, E)-dioxime cobalt(III) complex [Co(HL)₂pyCl]containing four 23-membered macrocyclic ionophores has beenprepared. The cobalt(III) complex [Co(LBF₂)₂pyCl]bridged with BF₂ ⁺ was prepared using the precursorcobalt(III) complex and boron trifluoride ethyl ethercomplex. The solvent extraction of heavy metal cationssuch as Ni²⁺, Cu²⁺, Zn²⁺, Hg²⁺ and Pb²⁺ by the BF₂ ⁺-capped cobalt(III) complex has been investigated. The structure of the complexes is proposedaccording to elemental analyses, ¹H and ¹³C-NMR, IRand mass spectral data.     

Polymer complexes. LV. Spectroscopic,thermal studies,and coordination of metal ions N-[3-(5-amino-1,2,4-triazolo)] acrylamide polymer complexes

Novel polymeric complexes with a potentially bidentate ligand formed by amidation of 3,5-diamino-1,2,4-triazole with acryloyl chloride were synthesized and characterized on the basis of elemental analyses, IR, ¹H-NMR, UV-Vis, magnetic susceptibility measurements, molar conductance, and thermal analyses. The molar conductance data reveal that all the polymer complexes are non-electrolytes. Spectral studies reveal that the free ligand coordinates bidentate to the metal ion through the oxygen of the carbonyl and azomethine of the heterocyclic ring. Elemental analyses of the polychelates indicate the metal to ligand ratio of 1?:?1/1?:?2. On the basis of electronic spectral data and magnetic susceptibility measurements, suitable geometry has been proposed for each polymeric complex. The electron spin resonance spectral data of the Cu(II) complex showed that the metal–ligand bonds have considerable covalent character. The thermal behavior of these chelates shows that the polymer complexes lose coordinated water in the first step immediately followed by decomposition of the anions and ligand molecules in a subsequent step.     

Synthesis of new lariat cyclicdiamides and their metal complexes

Three new lariat dilactam host molecules were prepared by the reaction of triethyleneglycol dicarboxylic acid dichloride withN,N-disubstitutèd-4,7-dioxa-1,10-diazadecane precursors. The amide nitrogen pivot of such compounds are substituted with the benzyl, octyl and dodecyl groups. The complexing ability of these dilactams is displayed with a series of metal complexes of Na⁺, K⁺, Ca²⁺, Sr²⁺, Pb²⁺ and Ag⁺ ions. The structures determined are consistent with the data of¹H-NMR,¹³C-NMR, IR spectra and elemental analyses.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August, 1995.     

Lanthanide complexes derived from hexadentate macrocyclic ligand: Synthesis,spectroscopic and thermal investigation

The lanthanide complexes derived from (3,5,13,15-tetramethyl 2,6,12,16,21-22-hexaazatricyclo[15.3.I^1-17I^7-11]cosa-1(21),2,5,7,9,11(22),12,15,17,19-decane) were synthesized. The complexes were found to have general composition [Ln(L)X₂·H₂O]X, where Ln = La³⁺, Ce³⁺, Nd³⁺, Sm³⁺ and Eu³⁺ and X = NO₃^? and Cl^?. The ligand was characterized by elemental analyses, IR, Mass, and ¹H NMR spectral studies. All the complexes were characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, Mass, electronic spectral techniques and thermal studies. The ligand acts as a hexadentate and coordinates through four nitrogen atoms of azomethine groups and two nitrogen of pyridine ring. The lanthanum complexes are diamagnetic while the other Ln(III) complexes are paramagnetic. The spectral parameters i.e. nephelauxetic ratio (β), covalency factor (b^1/2), Sinha parameter (δ%) and covalency angular overlap parameter (η) have been calculated from absorption spectra of Nd(III) and Sm(III) complexes. These parameters suggest the metal–ligand covalent bonding. In the present study, the complexes were found to have coordination number nine.     

Polymer complexes. LXXVI. Synthesis,characterization, CT‐DNA binding,molecular docking and thermal studies of sulfoxine polymer complexes

Novel polymer complexes of 8‐hydroxyquinoline‐5‐sulfonic acid hydrate ( H ₂ L ) with Cu²⁺, Co²⁺ and Ni²⁺ chloride were prepared and characterized. Microanalysis, magnetic susceptibility, IR spectra, electron spin resonance, mass spectra, X‐ray, molar conductance, thermal, and UV–Vis spectra studies have been used to confirm the structure of the prepared polymer complexes. The molecular and electronic structures of the hydrogen bond conformers for ligand ( H ₂ L ) were optimized theoretically and the quantum chemical parameters were calculated. On the basis of elemental and IR data, the chemical structure of metal chelates commensurate that the tri‐dentate (H₂L) coordinate to metal chlorides through oxygen atom of phenolic OH and oxygen atom of SO₃‐H group by replacing H atoms and nitrogen of the quinoline ring. The magnetic studies suggested the octahedral geometrical structure for all produced polymer complexes with general formula {[ML (OH₂)₃] .xH₂O}_n (M = Cu²⁺, x = 1.; Co²⁺, x = 2 and Ni²⁺, x = 2) in molar ratio (1:1). Coats–Redfern and Horowitz–Metzger methods have been used for calculating the activation thermodynamic parameters of the thermal decomposition for H ₂ L and its polymer complexes. The interaction between H ₂ L and its transition metal complexes with the calf thymus DNA (CT‐DNA) was determined by UV–Vis spectra. Binding efficiency between H ₂ L with the receptors of the prostate cancer (PDB code 2Q7L Hormone) and the breast cancer (PDB code 1JNX Gene regulation) was studied by molecular docking. The inhibition behaviour of H ₂ L against the corrosion of carbon steel / HCl (2 M) solution was studied by weight loss, Tafel polarisation, electrochemical impedance spectroscopy (EIS) and electrochemical frequency modulation (EFM) techniques. The adsorption isotherm was found to be Friendlish isotherm. The morphology of inhibited carbon steel? s surface was studied using scanning electron microscope (SEM) and energy dispersive X‐ray spectroscopy (EDS).     

Synthesis,characterization, aggregation and thermal properties of a novel polymeric metal-free phthalocyanine and its metal complexes

A novel polymeric metal-free phthalocyanine (M = 2H) and its metal complexes (M = Zn, Cu, Co and Ni) were prepared by the tetramerization reaction of 3,6,9-Tris(p-tolylsulfonyl)-1,11-bis(3,4-dicyanophenoxy)-3,6,9-triazaundecane 5 with the appropriate materials. The electrical conductivities of the metal-free phthalocyanine and the metal complexes, measured in air, were found to be ∼10⁻⁶–10⁻⁵ S m⁻¹. The aggregation property of the zinc complex 7 was investigated with Ni²⁺, Cu²⁺, Co²⁺, Pb²⁺, Cd²⁺ and Ag⁺ cations. Thermal analysis of the polymers were done by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) at a heating rate of 10 °C min⁻¹ under a nitrogen atmosphere. All the novel compounds were characterized by using elemental analysis, UV–Vis, FT–IR, NMR and MS spectral data and DSC, DTA/TG techniques.     

Synthesis and spectroscopic studies of biologically active tetraazamacrocyclic complexes of Mn(II), Co(II), Ni(II), Pd(II) and Pt(II)

Complexes of Mn(II), Co(II), Ni(II), Pd(II) and Pt(II) were synthesized with the macrocyclic ligand, i.e., 2,3,9,10-tetraketo-1,4,8,11-tetraazacycoletradecane. The ligand was prepared by the [2 + 2] condensation of diethyloxalate and 1,3-diamino propane and characterized by elemental analysis, mass, IR and ¹H NMR spectral studies. All the complexes were characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, IR, electronic and electron paramagnetic resonance spectral studies. The molar conductance measurements of Mn(II), Co(II) and Ni(II) complexes in DMF correspond to non electrolyte nature, whereas Pd(II) and Pt(II) complexes are 1:2 electrolyte. On the basis of spectral studies an octahedral geometry has been assigned for Mn(II), Co(II) and Ni(II) complexes, whereas square planar geometry assigned for Pd(II) and Pt(II). In vitro the ligand and its metal complexes were evaluated against plant pathogenic fungi (Fusarium odum, Aspergillus niger and Rhizoctonia bataticola) and some compounds found to be more active as commercially available fungicide like Chlorothalonil.