Synthesis and physicochemical studies on Co(III) complexes

Complexes of Co(III) with 2-hydroxyacetophenone-thiosemicarbazone, 2-hydroxy-3-methylacetophenonethiosemicarbazone and 2-hydroxy-4-methyl-acetophenonethiosemicarbazone, and the addition complexes of 2-hydroxy-acetophenone thiosemicarbazone with ammonia, pyridine, aniline,o-toluidine,m-toluidine andp-toluidine have been synthesized and characterized on the basis of their conductivities, electronic and infrared spectral data. All complexes are low-spin octahedral in nature. Various parameters have been obtained using ligand field theory.     

Reactions of dichlorobis(cyclopentadienyl)titanium (IV) with multidentate Schiff bases

Summary Dichlorobis(cyclopentadienyl)titanium(IV), Cp₂TiCI₂, reacts with bidentate Schiff bases such as salicylideneaniline, salicylidene-o-toluidine, salicylidene-m-toluidine, salicylidene-p-toluidine and 2-hydroxy-l-naphthylReprints of this paper are not available.To whom all correspondence should be addressed.     

Thermochemical studies for determination of the molar enthalpy of formation of aniline derivatives

The standard (p ^o=0.1 MPa) molar enthalpies of combustion atT=298.15 K were measured by static bomb combustion calorimetry for liquidN,N-diethylaniline,N,N-dimethyl-m-toluidine,N,N-dimethyl-p-toluidine, andN-ethyl-m-toluidine. Vaporization enthalpies forN,N-dimethyl-m-toluidine andN-ethyl-m-toluidine were determined by correlation gas chromatography. Derived standard molar values of _f H _m ^o (g) at 298.15 K forN,N-diethylaniline (62.1±7.6);N,N-dimethyl-m-toluidine (72.6±7.3),N,N-dimentyl-p-toluidine (68.9±7.4),N-ethyl-m-toluidine (30.5±3.8 kJ· mol^–1) were obtained.     

Nachweis isomerer Chloraniline und ihrer Derivate

Zusammenfassung 2,4-Dinitrofluorbenzol liefert mit p-Chloranilin eine Indikatorsäure, mit m-Chloranilin reagiert es nur in geringem Maß, aber mit der o-Verbindung gibt es keine Reaktion. Die mit diazotierter Sulfanilsäure hergestellten Diazoverbindungen von o- und p-Chloranilin sind Indikatorsäuren, die von m- bzw. 2,5-Dichloranilin sind amphotere Indikatoren. Mit jener Reaktion kann p-Chloranilin, mit dieser m-Chloranilin bzw. 2,5-Dichloranilin neben ihren Isomeren nachgewiesen werden. 5-Chlor-o-toluidin liefert mit diazotierter Sulfanilsäure eine Indikatorbase, aber 4-Chlor-o-toluidin bzw. 4-Chlor-o-anisidin Indikatorsäuren; damit kann man 5-Chlor-o-toluidin neben 4-Chlor-o-toluidin bzw. 5-Chlor-o-anisidin nachweisen. Mit diazotiertem Anilin gibt 5-Chlor-o-anisidin eine starke Indikatorsäure; damit kann es neben 5-Chlor-o-toluidin nachgewiesen werden. 4-Chlor-o-toluidin bildet mit diazotiertem p-Nitroanilin eine Indikatorsäure, aber 4-Chlor-2-nitroanilin gibt keine Reaktion. Auf der Basis dieses Verhaltens kann 4-Chlor-o-toluidin neben 4-Chlor-2-nitroanilin nachgewiesen werden. 4-Chlor-2-nitroanilin gibt dagegen mit diazotiertem p-Phenetidin eine Indikatorsäure. Auf der Grundlage dieser Indikatorwirkung kann man 4-Chlor-2-nitroanilin neben 4-Chlor-2-toluidin nachweisen.

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Summary 2,4-Dinitrofluorobenzene yields an indicator acid withp-chloraniline; it reacts to only a slight extent withm-chloraniline, but it gives no reaction with theo-compound. The diazo compounds ofo- andp-chloraniline produced by means of diazotized sulfanilic acid are indicator acids, those from them- andp-chloraniline are amphoteric indicators.p-Chloraniline can be detected by means of the former reaction, andm-chloraniline or 2,5-dichloroaniline can be detected in the presence of their isomers by the latter reaction. With diazotized sulfanilic acid, 5-chloro-o-toluidine yields an indicator base, but 4-chloro-o-toluidine or 4-chloro-o-anisidine yield indicator acids; accordingly, 5-chloro-o-toluidine can be detected in the presence of 4-chloro-o-toluidine or 5-chloro-o-anisidine. With diazotized aniline, 5-chloro-o-anisidine produces a strong indicator acid; it may be detected in this manner in the presence of 5-chloro-o-toluidine. An indicator acid is produced by 4-chloro-o-toluidine with diazotizedp-nitraniline, but 4-chloro-2-nitraniline gives no reaction. 4-Chloro-o-toluidine may be detected on the basis of this behavior in the presence of 4-chloro-2-nitraniline. On the other hand, 4-chloro-2-nitraniline yields an indicator acid with diazotizedp-phenetidine. 4-Chloro-2-nitraniline can be detected in the presence of 4-chloro-2-toluidine on the basis of this indicator action.

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Résumé Le dinitro-2,4-fluorobenzène donne avec lap-chloroaniline un indicateur sous forme acide; il ne réagit que dans une faible mesure avec lam-chloroaniline; il ne donne aucune réaction avec le composé ortho. Les composés diazoïques de l'o et de lap-chloroaniline préparés avec l'acide sulfanilique diazoté sont des indicateurs sous forme acide, ceux de lam ou de la dichloro-2, 5-aniline à l'aide de la première réaction, ou avec celle de lam-chloroaniline ou de la dichloro-2,5-aniline, en présence de leurs isomères. La chloro-5-o-toluidine donne avec l'acide sulfanilique diazoté un indicateur sous forme basique, alors que la chloro-4-o-toluidine ou la chloro-4-o-anisidine conduisent à des indicateurs sous forme acide; on peut donc rechercher ainsi la chloro-5-o-toluidine en présence de chloro-4-o-toluidine ou de chloro-5-o-anisidine. La chloro-5-o-anisidine donne avec l'aniline diazotée un indicateur sous forme acide; on peut ainsi en faire la recherche en présence de chloro-5-o-toluidine. La chloro-4-o-toluidine forme avec lap-nitroaniline diazotée un indicateur sous forme acide, mais la chloro-4-nitro-2-aniline ne donne pas de réaction. En mettant à profit cette différence de comportement, on peut faire la recherche de la chloro-4-o-toluidine en présence de la chloro-4-nitro-2-aniline. La chloro-4-nitro-2-aniline donne par contre un indicateur sous forme acide avec lap-phénétidine diazotée. Cette action en tant qu'indicateur permet la recherche de la chloro-4-nitro-2-aniline en présence de chloro-4-o-toluidine.

     

Chromaticity of poly(o-toluidine) matrix enhanced by anion-exchange mechanism

The incorporation of 9,10-anthraquinone-1,5-disulfonate (AQS₂) into the protonated form of poly(o-toluidine) (POT), produced by oxidative polymerization of the cationic form of the monomer or by doping the basic form (POT-EB) by anion-exchange has been studied by FTIR and UV-VIS spectroscopy and mass spectrometry. The presence of sulfur and the absence of chlorine proven by elemental analysis of the polymer product confirmed the substitution of the chloride anion with AQS₂ in the matrix. Molecular mechanics (MM+) calculations suggest that the optimal geometric structure (OMG) of AQS₂-doped POT is at least three (3.92) times more stable than that of the parent chloride-doped POT (HCl-doped POT). The increase of the absorbance at about 840 nm associated with the increasing concentration of AQS₂ revealed the insertion of AQS₂ into the POT chain. This observation could be explained by the diffusion of AQS₂ in the polymer chain. Kinetic parameters of the oxidative polymerization of the cationic form of o-toluidine (o-T-HClO₄) in the presence of different amounts of AQS₂ were deduced on the basis of absorbance variations. The results of computer-oriented kinetic analysis indicate that the rate-controlling step of the o-T polymerization is governed by the Ginstling-Bronstein equation representing the three-dimensional diffusion (D4). Activation parameters of the oxidative polymerization of protonated o-T in the presence of varying amount of AQS₂ were computed and discussed.     

Synthesis,spectroscopic (IR,electronic, FAB-mass,and PXRD), magnetic,and antimicrobial studies of new iron(III) complexes containing Schiff bases and substituted benzoxazole ligands

Mixed ligand complexes of iron(III), [Fe(sb)₂(py)Cl]?·?2H₂O (1–9) [where sbH?=?Schiff bases (derived from condensation of 2-aminopyridine (sapH), 2-aminophenol (saphH), o-toluidine (o-smabH), aminobenzene (sabH), p-toluidine (p-smabH), 3-nitroaniline (snabH), and anthranilic acid (saaH) with salicylaldehyde and substituted (mercapto-)benzimidazole (mbzH), {2-(o-hydroxyphenyl)}benzoxazole, (pboxH)], have been synthesized by the interactions of iron(III) chloride with corresponding ligands in 1?:?2 molar ratio in refluxing pyridine. These complexes have been characterized by elemental analyses, melting points, spectral, and magnetic studies. Powder X-ray diffraction studies of some representative complexes are also reported herein. The antibacterial and antifungal activities of the free ligands and their iron(III) complexes were found in vitro. The complexes showed good antibacterial and antifungal effect to some bacteria and fungi. Two standard antibiotics (chloromphenicol and terbinafine) were used for comparison with these complexes.     

Synthesis and spectral characterization of some complexes of platinum(II) containing η-methyleugenol

Several complexes of the formula trans-[Pt(Meug)(Am)Cl₂], Meug: methyleugenol (4-allyl-1,2-dimethoxybenzene), a η²-coordinated olefin, and Am: ammine, methylamine, diethylamine, o-toluidine, m-toluidine, p-toluidine, o-anisidine, m-anisidine and p-anisidine have been prepared. UV, IR, Raman, ¹H NMR, ¹³C NMR and 2D NMR spectra of the complexes were recorded and analyzed.     

Synthesis, structural characterization, and antifungal activity of Schiff bases and their transition metal mixed-ligand complexes

Mixed-ligand complexes of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) have been prepared with biologically active Schiff bases, viz. potassium salt of o-hydroxyacetophenoneglycine [KHL] and bis(benzylidene)ethylenediamine [A¹] or thiophene-o-carboxaldene-p-toluidine [A²]. The synthesized mixed-ligand complexes have been characterized on the basis of elemental analysis, thermogravimetric analysis, magnetic measurements, and electronic and infrared spectra. The mixed-ligand complexes show higher antifungal activity as compared to the free ligands, metal salts, and the control (dimethylsulfoxide) but moderate activity as compared to the standard fungicides (bavistin and emcarb). This text was submitted by the authors in English.     

A viscometric study of tuning micellar morphology by organic additives

The micellar morphology in aqueous 0.2 M sodium dodecyl sulfate (SDS) solutions has been studied in the simultaneous presence of organic salts (anilinium hydrochloride, AHC; ortho-toluidine hydrochloride, oTHC; para-toluidine hydrochloride, pTHC) and aliphatic alcohols (n-butanol, C₄OH; n-pentanol, C₅OH; n-hexanol, C₆OH; n-heptanol, C₇OH), aliphatic amines (n-butylamine, C₄NH₂; n-pentylamine, C₅NH₂; n-hexylamine, C₆NH₂; n-heptylamine, C₇NH₂), or hydrocarbons (n-hexane, C₆H; n-heptane, C₇H) by viscosity measurements under Newtonian flow conditions at 30 °C. Addition of alcohols and amines causes micellar growth which is found to be dependent upon chain length of the additive and nature of organic salt counterion. It is observed that amines are more effective in increasing the viscosity of the system if added in pure 0.2 M SDS solution, while SDS + pTHC system was found versatile when alcohols were added to this system. The increased viscosity or the micellar growth is explained in terms of the site of solubilization of the respective additive and the interaction of the additive with micellar surface and salt counterion present in the head group region. Hydrocarbons are nearly ineffective in inducing micellar growth and can be used as ‘micellar destroyer’ for the grown micelles. The additives used are found effective in tuning the environment of the micelle which is reflected in viscosity behavior. This work may find use in micellar ultrafiltration as well as in mimicking the natural cell, which has several aspects common with the micelle.     

Lanthanon (III) Derivatives of Monofunctional Bidentate Schiff Bases

The 1:1, 1:2 and 1:3 interactions of lanthanon (III) isopropoxide with monofunctional bidentate Schiff bases as salicylidene-o-toluidine (SOTH) and salicylidene-p-p-toluidine (SPTH) have been investigated. The resulting products Ln(OPr¹)₂(SB), Ln(OPr¹)(SB)₂ and Ln(SB)₃ (where Ln=Pr, Nd and Sm and SB^1? is the anion of the corresponding Schiff base) have been isolated in almost quantitative yields. The infrared spectra of these compounds have been recorded and plausible structures suggested.     

Infrared spectra of soluble polytoluidines

IR spectra of soluble poly-o-toluidine (POT) and poly-m-toluidine (PMT) have been studied. Preliminary assignment of their IR spectra is given by comparing their spectra in HCl and I₂, doped states and in subsequently NH₃ dedoped state with that in intrinsic state.     

Quantitative analysis of a mixture of cresols by carbon-13 NMR spectroscopy

The suitability of ¹³C NMR as a technique for determining o-, m, and p-cresols in their mixtures was investigated. Spectra were determined in methanol, containing o-toluidine as an internal standard, without nuclear Overhauser suppression. Ratios of peak areas of each cresol isomer to o-toluidine were determined by means of the standard calibration method, and then mixtures of cresol isomers were prepared and quantified in varying concentrations from 8.30 to 66.84 mol% for each isomer, with an average absolute error of 0.78% for all isomers. The method described was convenient and the results were generally satisfactory.     

Kinetic analysis of thermogravimetric data. XVIII. Thermal decomposition of some [Co(AMINE)2 (NCS)2] type complexes

[Co(p-toluidine)₂(NCS)₂] (I), [Co(m-toluidine)₂(NCS)₂] (II) and [Co(aniline)₂(NCS)₂] (III) have been synthesized. Kinetic parameters n, E and Z (apparent reaction order, activation energy and pre-exponential factor) have been derived from the TG curves recorded under 12 different working conditions. The influence of the sample weight (m_o) and of the heating rate (q) upon the kinetic parameters as well as upon the decomposition temperature and the amount of amine liberated in the first decomposition stage are discussed. Mean values of the activation energy and of the decomposition temperature are discussed in terms of the Co—amine bond strength and molecular structure based on IR evidence.     

Comparative studies of chemically synthesized polyaniline and poly(o-toluidine) doped with p-toluene sulphonic acid

Polyaniline and poly(o-toluidine) doped with p-toluene sulphonic acid (p-TSA) were synthesized by in situ chemical polymerization method using ammonium per sulphate as an oxidizing agent. This is a novel polymerization process for the direct synthesis of emeraldine salt phase of the polymer. The polymers were characterized by using UV-Vis and FT-IR spectroscopy, SEM, elemental analyzer, TGA/DSC and conductivity measurements. Thermal analysis shows that poly(o-toluidine) is less thermally stable compared to polyaniline. The less conductivity in poly(o-toluidine) is due to the cumulative steric as well as electronic effect of the bulky methyl substituent present on the benzene ring. High temperature conductivity measurements show ‘thermal activated behavior’.     

Porous copolymer-based cation exchanger for the off-line preconcentration of aromatic amines from water

Summary A weakly polar porous copolymer and the sulfonic acid cation exchanger based on this copolymer were tested as sorbents for off-line preconcentration of aromatic amines from water. Minicolumns packed with the 1,4-di(methacryloyloxymethyl)naphthalene—divinylbenzene copolymer and the cation exchanger were used for the solid-phase extraction of polar amines. In order to study the sorption properties of these polymeric materials, the recoveries and breakthrough volumes ofp-aminophenol,o, m andp-phenylenediamine, aniline,o andp-anisidine,p-nitroaniline, ando-toluidine were determined.     

Electrochemical and chemical synthesis of nanostructure copoly(aniline-o-anisidine-o-toluidine) and study of its electrochemical behavior in organic sulfonic acid media

Terpolymerization of aniline, o-anisidine and o-toluidine was carried out by electrochemical and interfacial chemical polymerization. All homopolymers and terpolymer thin films have been synthesized through electropolymerization at room temperature in aqueous solutions containing 0.5 M of organic sulfonic acid, such as p-toluene sulfonic acid, methane sulfonic acid, sulfosalicylic acid, dodecylbenzene sulfonic acid, and 0.1 M of aniline, o-anisidine and o-toluidine monomers, using cyclic voltammetry method, applying a sequential linear potential scan at a rate of 25 mV s^?1 between ?0.1 and 0.9 V. The electrochemical terpolymerization has been performed at various mole ratios of monomers. Nanoparticles obtained from conjugation of homo- and terpolymer with organic sulfonic acids, were prepared by a chemical oxidation via interfacial chemical polymerization. SEM micrographs, FTIR spectra and conductivity measurements using four-probe method were applied for the characterization of the products. Terpolymer was characterized by higher conductivity than poly-o-toluidine and lesser than polyaniline and poly-o-anisidine. The solubility of terpolymers was dependent on the monomers mole ratio.     

Investigation of Micellar and Phase Separation Phenomenon of the Amphiphilic Drug Amitriptyline Hydrochloride with Cationic Hydrotropes

Micellization and phase separation of the amphiphilic drug amitriptyline hydrochloride (AMT) in the absence and presence of cationic hydrotropes (aniline hydrochloride, para-toluidine hydrochloride, and ortho-toluidine hydrochloride) have been investigated in the present study. The experimental critical micelle concentration (cmc) values are lower than cmc ^id values (cmc ^id is the cmc value at ideal mixing state), indicating attractive interactions between the two components (drug and hydrotrope) in mixed micelles. The bulk behaviors were investigated using the different theoretical models of Clint, Rubingh, Motomura, and Rodenas for comparison of the results of different binary combinations of the drug and hydrotropes. Synergistic interactions were confirmed in all binary combinations at all temperatures, which increase with increasing concentration of hydrotropes. Activity coefficients (f ₁ and f ₂) were found to be consistently less than unity indicating nonideality in the systems. At a fixed drug concentration (50 mmol·dm^?3) and pH (6.7), the hydrotropes showed a continuous increase in the cloud point. Thermodynamic parameters were also evaluated and discussed in detail.     

Chelating Behaviour of Substituted 1-Benzoyl-4-Phenylthiosemicarbazide

The preparation and characterization of a series of new coordination compounds of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) containing o-methyl- or o-chlorobenzoyl-4-phenyl-3-thiosemicarbazide (HMBPT, HCBPT=HL) are reported. The reaction products were investigated by analyses, electrolytic conductance, magnetic susceptibility, reflectance and IR spectral studies. The IR spectra show that HMBPT and HCBPT coordinate with the metal ions via different coordination sites (NS and/or NO). The spectral data support the suggestion that the ligands form his-chelates with Ni(II) and Cu(II) of square planar stereochemistry and of general formulae ML₂·H₂O, where L is the uninegatively charged bidentate ligand. The Co(II) ion forms octahedral and tetrahedral structures with HMBPT and HCBPT, respectively. The ligand field parameters (D₄, B and β) for the Co(II) chelates were calculated using the averaged-ligand-field approximation. The influence of the benzene ring substituents (o-chloro or o-methyl) on the stereochemistry are discussed. Also, the formation of the complexes in solution was tested by the pH-metric method.     

A new synthesis of 2,1-benzisothiazoles

A novel synthesis of 2,1-benzisothiazoles is described. When an o-toluidine or N-sulfinyl-o-toluidine is allowed to react with an N-sulfinylsulfonamide, a 2,1-benzisothiazole is formed.     

In situ synthesis of copper nanoparticles and poly(o-toluidine): A metal-polymer composite material

We report here a novel in situ synthetic method for the preparation of poly(o-toluidine) and copper nanoparticle composite material. In this experiment, o-toluidine and cupric sulfate were used as the precursor; during the reaction o-toluidine was oxidized and forms poly(o-toluidine), while on the other hand cupric sulfate gets reduced and forms copper nanoparticle. IR, UV-vis and Raman spectra provide the information on the structure of the polymer. The TEM and SEM show the size of the nanoparticles and the morphology of the polymer, respectively.