1H-, 13C-, 19F-, 31P-NMR-Charakterisierung der Produkte der Alkoholyse von Trichlorophosphazen-N-Phosphoryldichlorid durch Trifluoroethanol

¹H, ¹³C, ¹⁹F, ³¹P N.M.R. Characterization of the Alcoholysis Products of Trichlorophosphazene-N-phosphoryldichloride by Trifluoroethanol Since polychlorophosphazenes can be obtained by polycondensation of P₂NOCl₅ the classical substitution of Cl by CF₃CH₂O in these polymers was transposed to P₂NOCl₅. The formation of mono, di, or pentaester depends on the molar ratio of the reactants. By reaction of CF₃CH₂OH on the pentaester a tetrasubstituted derivative of tetrachlorodiphosphorylimid is obtained. All products are characterized by mass spectroscopy and ¹H, ¹³C, ¹⁹F, and ³¹P n.m.r.     

Beitrag zur Chemie der Phosphor-Stickstoff-Verbindungen Reaktion von Cl3PN?P(O)Cl2 mit Tetrahydrofuran

Contribution to the Chemistry of Phosphorus Nitrogen Compounds. Reaction of Cl₃P?N? P(O)Cl₂ with Tetrahydrofuran As well as many phosphorus compounds, the trichlorophosphazene phosphoryldichloride Cl₃P?N? P(O)Cl₂ reacts at 30°C with a large excess of tetrahydrofuran to give the polytetrahydrofuran. Otherwise, if we use higher molecular ratios Cl₃P?N? P(O)Cl₂/THF (respectively 1/3 and 1) we obtain at 30°C beside polytetrahydrofuran the N chlorobutylimidodiphosphoryltetrachloride. This last compound is the main one obtained at 60°C and is probably formed by rearrangement of the O chlorobutyl isomer. However the formation of small quantities of polytetrahydrofuran chains linked with phosphorus cannot be avoided.     

Direct arylation of oxazole and benzoxazole with aryl or heteroaryl halides using a palladium-diphosphine catalyst

Through the use of PdCl(dppb)(C₃H₅) as a catalyst, a range of aryl bromides and chlorides undergoes coupling via C-H bond activation/functionalization reaction with oxazole or benzoxazole in good yields. This air-stable catalyst can be used at low loadings with several substrates. Surprisingly, better results in terms of substrate/catalyst ratio were obtained in several cases using electron-excessive aryl bromides than with the electron-deficient ones. This seems to be mainly due to the relatively low thermal stability of some of the 2-arylbenzoxazoles formed with electron-deficient aryl halides. With these substrates, in order to obtain higher yields of product, the reactions had to be performed at a lower temperature (100-120 °C) using a larger amount of catalyst. On the other hand, in the presence of the most stable products, the reactions were performed at 150 °C using as little as 0.2 mol% catalyst. Arylation of benzoxazole with heteroaryl bromides also gave the coupling products in moderate to high yields using 0.2-5 mol% catalyst. With this catalyst, electron-deficient aryl chloride such as 4-chlorobenzonitrile, 4-chloroacetophenone or 2-chloronitrobenzene have also been used successfully.     

Synthesis,characterization, electrochemical behaviour and catalytic activity of manganese(II) complexes with linear and tripodal tetradentate ligands derived from Schiff bases

New manganese(II) complexes, [Mn(H₂L)(H₂O)₂]Cl₂· xH₂O, with linear and tripodal tetradentate ligands have been synthesized and characterized by elemental analysis, molar conductance, i.r. spectra, magnetic measurements and electronic and e.s.r. spectra. The data show that the ligands are neutral and coordinate to manganese in a tetradentate manner; the other axial sites are occupied by the water molecules. Magnetic and e.s.r. data show that manganese(II) adopts a high-spin configuration in the complexes. The electrochemical behaviour of the complexes, determined by cyclic voltammetry, shows that the chelate structure, ligand geometry and electron donating effect of the ligand substituents are among the factors influencing the redox potentials of the complexes. In addition, we note that linear ligands stabilize the manganese(III) state to a greater extent than tripodal ligands and their complexes vigorously catalyse the disproportionation of hydrogen peroxide in the presence of added imidazole.     

Corrosion inhibition of steel in 0.5 M H2SO4 by [(2-pyridin-4-ylethyl)thio]acetic acid

The influence of [(2-pyridin-4-ylethyl)thio]acetic acid (P1) and pyridine (P2) on the corrosion inhibition of steel in sulphuric acid solution is studied using weight loss, potentiodynamic polarisation and linear polarisation resistance (R_p) and electrochemical impedance spectroscopy (EIS) measurements. Results obtained show that P1 is the best inhibitor and its inhibition efficiency (E%) increases with the increase of concentration. The highest E% of 82% is observed at 5 × 10⁻³ M. Potentiodynamic polarisation studies clearly reveal that P1 acts as a mixed inhibitor. The inhibitor studied reduces the corrosion rates. E% values obtained from various methods used are in good agreement. Adsorption of P1 on steel surface obeys to Langmuir adsorption isotherm. Effect of temperature indicates that E% decreases with temperature between 298 and 353 K.     

Synthesis,characterization, and biological activities of oxovanadium(IV) and cadmium(II) complexes with reduced Schiff bases derived from <Emphasis Type="Italic">N,N′</Emphasis>-<Emphasis Type="Italic">o</Emphasis>-phenylenebis(salicylideneimine)

New oxovanadium(IV) and cadmium(II) complexes with reduced Schiff bases derived from N,N′-o-phenylenebis(salicylideneimine) have been synthesized and characterized using infrared and UV-visible spectra, ESR, and thermogravimetry. The complexes were identified as [ML] · (H₂O) species, where deprotonated ligands are coordinated to metal through N₂O₂ donor atoms. Antioxidant activity of the ligands and complexes was evaluated, revealing that the complexes exhibit a higher scavenging activity than the corresponding ligands. The prepared cadmium complexes showed slightly higher activity than the vanadium ones. Antifungal activity was tested against different human fungi including yeasts of the Candida genus (C. albicans and C. glabrata) and an opportunistic mould Aspergillus fumigatus. The oxovanadium complexes exhibited a very low activity toward C. albicans while the cadmium ones showed a significant growth inhibition of all the fungi tested; mainly of A. fumigatus though this mould is poorly susceptible to current antifungal agents like Itraconazole.     

Synthesis,characterisation and antifungal activity of a series of Cobalt(II) and Nickel(II) complexes with ligands derived from reduced <Emphasis Type="Italic">N</Emphasis>, <Emphasis Type="Italic">N</Emphasis>′-<Emphasis Type="Italic">o</Emphasis>-Phenylenebis(Salicylideneimine)

The synthesis and characterisation by elemental analysis, conductivity, FTIR, UV–Visible, ESR and magnetic measurements are described for a series of complexes of nickel(II) and cobalt(II) with three ligands (H₂L^1–3) derived from reduced N, N′-o-Phenylenebis(salicylideneimine). The complexes formed are identified as neutral species, where the ligands are coordinated through N and O donor atoms. The formulae obtained for the complexes are: [CoL(H₂O)₂] with octahedral geometry and [NiL] with tetrahedral geometry. Their antifungal activity is evaluated towards human pathogenic fungi including yeasts of the Candida genus, some opportunistic moulds belonging to the Aspergillus, Scedosporium genus and some dermatophytes. The cobalt complexes show a significant growth inhibition of yeasts tested and also to fungi of the genus Scedosporium which is of interest because these fungi are usually poorly susceptible to current antifungal including Amphotericin B and Itraconazole, chosen as reference in this study. The activity data show that the metal complexes are more potent than the parent ligand.     

Corrosion inhibition of steel in sulphuric acid by pyrrolidine derivatives

Novel corrosion inhibitors, namely 1-{2-[(2-hydroxyethyl)thio]ethyl}pyrrolidin-2-one (P5) and {[2-(2-oxopyrrolidin-1-yl)ethyl]thio}acetic acid (P4), were synthesised and tested as corrosion inhibitors for steel in 0.5 M H₂SO₄. The effects of P4 and P5 are also compared to their initial reactants 1-vinylpyrrolidin-2-one (P1), 2-mercaptoethanol (P2) and mercaptoacetic acid (P3). The study was carried out by weight loss measurements, potentiodynamic polarisation, linear polarisation resistance (R_p) and electrochemical impedance spectroscopy (EIS) methods. The inhibition efficiency increases with the concentration of P5 to attain 89% at 5 × 10⁻³ M. We note good agreement between the various methods explored. Polarisation measurements show also that the pyrrolidones act essentially as cathodic inhibitors. The cathodic curves indicate that the reduction of proton at the steel surface is an activating mechanism. P4 and P5 adsorb on the steel surface according to Langmuir adsorption model. Effect of temperature is also studied in the 298-353 K range. Efficiency is explained by the theoretical studies.