Stability constants of D(−)-ribose complexes with calcium in diluted aqueous and methanolic solutions

The study of D(?)-ribose complexing with calcium in aqueous solutions less than 1.64 × 10^?1M by potentiometric measurements with a calcium selective electrode afforded the value of K₁ = 1.70 liters × mole^?1 (SD = 1.05 × 10^?3). Numerical analysis indicated that complex species with 1:1 and 1:2 calcium to D(-)-ribose ratios are present simultaneously: k₁ = 1.13 liters × mole^?1 and K₂ = 8.47 liters × mole^?1 (SD = 0.95 × 10^?3).In methanolic medium 1.24 × 10^?2M with regard to calcium chloride both stoichiometric proportions were evidenced. A large error accompanying the stability constant K₁ = 28 kg × mole^?1 (RSD = 82%) renders unreasonable the K₂ value obtained from the product K₁ × K₂ = 96.5 kg² × mole^?2.The results are discussed with respect to the data published for more concentrated (1.27 M) aqueous solutions obtained on the basis of ₁H-NMR spectroscopic investigations.     

β-Tricarbonyl compounds. I. 2,4-Disubstituted 1,3-cyclopentanediones

Summary Stable enolic isomers of 2-aroyl-4-aracyl-1,3-cyclopentanediones such as3 and4 were prepared by condensation of aryl methyl ketones and diethyl maleate using an excess of sodium ethoxide (Aryl=C₆H₅, 4-C₆H₄CH₃, 4-C₆H₄Br and 4-C₆H₄Cl).

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-Tricarbonyl Verbindungen. I. 2,4-Disubstituierte 1,3-Cyclopentandione

Zusammenfassung Stabile Enol-Isomere von 2-Aroyl-4-aracyl-1,3-cyclopentandionen wie3 und4 wurden durch Kondensation von Arylmethylketonen und Diethylmaleat mit einem Überschuß von Natriumethoxid dargestellt (Aryl=C₆H₅, 4-C₆H₄CH₃, 4-C₆H₄Br und 4-C₆H₄Cl).

     

Fluorescence Characteristics of Schiff Bases Derived from Amino- and Aminoalkylpyridines

The fluorescence characteristics of the Schiff bases 2-(3-pyridylmethyliminornethyl)phenol (1), 2-(2 pyridyliminomethyl)phenol (2), N.N-bis(salicylidene)-2,3-pyridinediamine (3), N,N'-bis(salicylidene)-2,6-pyridinediamine (4) and 2-(2-amino-4-methoxymethyl-6-methyl-3-pyridylmethyliminomethyl)phenol (5) were studied in various solvents at different pH values. Corresponding quantum efficiencies were determined. Compound 1, which showed a tendency towards tautomeric mterconversion to ketoamine in polar protic solvents, was not fluorescent at pH < 8. The fluorescence of other compounds was very sensitive to solvent polarity and the pH of the medium. Compounds 2-4, preferably present as enolimines in all solvents, were not fluorescent in non-polar and moderately polar solvents, whereas weak emission was observed in polar solvents, like methanol, dimethylformamide and dioxane/water 1/1 (0.001 < Q < 0.072). A significant increase in Stokes shifts and in quantum efficiencies was noted as a result of increasing polarity of dioxane/water mixtures, indicating specific interactions with polar water molecules. The emission was promoted at acidic pH values where a pyridinium cation was formed (0.061 < Q < 0.519, in dioxane/water 1/1 at pH 3.4). Compound 5, which was a tautomeric mixture of enoiimine and cyclic diamine in all solvents, was fluorescent in polar as well as in non-polar media. The quantum efficiency varied dependent on the solvent and pH (0.023 <Q< 0.435). The cyclic diamine, i. e. the more rigid structure was supposed to be responsible for the fluorescence in non-polar and aprotic solvents as well as at neutral, and weakly basic pH values.     

The micro-volumetric determination of lead with thionalide and its application to the analysis of tin-base and lead-base alloys

The authors have elaborated an exact micro-volumetric method for the determination of lead with thionalide. The method has been successfully applied to the determination of lead in tin-base and lead-base alloys, following the isolation of lead as lead sulphate and its redissolution in ammonium acetate.     

Protonation equilibria and complex formation ability of 2-amino-3-aminomethyl-4,6-disubstituted pyridines

The protonation equilibria of 2-amino-3-aminomethyl-4,6-disubstituted pyridines were studied by potentiometric titrations and by UV and ¹³C NMR spectrometry. Protonation constants log K₁ and log K₂ potentiometrically determined for 4-methoxymethyl-6-methyl (8.959 and 5.778), 6-methoxymethyl-4-methyl (8.964 and 5.407), and 4,6-dimethyl derivative (9.141 and 6.604), were compared with the values obtained by the spectrometric methods. Complex formation of these compounds with Cu(II), Ni(II), Zn(II) and Co(II) was investigated in solution whereby the outstanding effect of the pH value was established and the presence of the species with 1 : 1 and 2 : 1 ligand to metal ratios confirmed. Stability constants obtained by potentiometric titrations show a decrease of the complex stability in the order Cu > Ni > Zn with respective log β₁ values of 5.85, 3.56 and 2.93. Series of complexes isolated in the crude state were characterized by elemental analyses and spectrometric data, the latter serving also as the basis for making an attempt at the discernment of the coordination mode and sites.