Infrared spectroscopic study of the structure of the tetrabutyl S-dithiopyrophosphate complex of silver

The structure of the complex Ag·TBDTPP (tetrabutyl S-dithiopyrophosphate) formed in HNO₃ medium was studied by IR and NMR methods. The complex is involved in the isomerization of TBDTPP in the presence of Ag⁺ and NO ₃ ⁻ ions. In the IR spectra, we observe the disappearance of P−O−P band and the occurrence of new absorption bands associated with P−S−P and P=O bonds. The silver ion is coordinated to the thiophosphoryl group of the isomer molecule. The influence of HNO₃ concentration on complex formation is discussed.     

Analysis of DTA curves and calculation of kinetic data using computer technique

Principles of two computer programs useful for the evaluation of heterogeneous kinetics are described.The first program ALANTA allows to obtain the non-isothermal kinetic curve from the shape of general DTA peak using the DTA-equation derived elsewhere¹.The second program SQUEST determines the kinetic mechanism which is the most appropriate to a given non-isothermal kinetic curve and evaluates the corresponding kinetic parameters. The program decides between 19 kinetic models and uses both integral and differential methods of evaluation.     

Über einige Eigenschaften von Zinkphosphiten mit Berücksichtigung ihrer Wasserstoffbrückenbindung

Zinc phosphites ZnPHO₃·2.5 H₂O, Zn₂H₂P₃H₃O₉·H₂O, Zn₃H₄P₅H₅O₁₅·1.5 H₂O, ZnH₂H₂P₂H₂O₆ have been studied at higher temperatures and by X-rays and molecular spectroscopy. Hydrates ZnPHO₃·2.5 H₂O and Zn₂H₂P₃H₃O₉·H₂O, when heated, yield an anhydrous salt. Thermal decomposition of dihydrogen triorthophosphite and tetrahydrogen pentaorthophosphite leads, before oxidation of the anion, to a mixture of zinc phosphite ZnPHO₃ and dihydrogen diorthophosphite ZnH₂P₂H₂O₆ and then after loss of water of constitution dihydrogen diorthophosphite converts to zinc diphosphite ZnP₂H₂O₅. The results of the thermal decomposition study were confirmed by X-ray investigation. Anhydrous zinc dihydrogen triorthophosphite Zn₂H₂P₃H₃O₉ and zinc diphosphite ZnP₂H₂O₅ were hitherto unknown. Infrared spectra confirmed the existence of hydrogen bonding in all the phosphites studied and in the case of zinc phosphite ZnPHO₃·2.5 H₂O exhibited a symmetry decrease of the anion PHO₃ ^2– from the point group C_3v to C_s. In the crystal lattice of ZnPHO₃·2.5 H₂O hydrogen bonding by water molecules participates, with polyorthophosphites hydrogen bonding shares in the production of anions and in the case of their hydrates there is in addition hydrogen bonding by water molecules.

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Rapid determination of ethylene glycol at toxic levels in serum and urine

The rapid gas chromatographic detection and determination of ethylene glycol in biological fluids is described. Phenylboronic acid in acetone was used for the esterification of glycol. The phenylboronates of ethylene glycol and 1,2-propylene glycol are not separated on a packed column of medium polarity (OV-17), but they can be separated on a non-polar column (OV-101). In both instances, 1,3-propylene glycol can be used as an internal standard. The method requires only 100 microliters of serum or urine and is suitable for trace analysis in an emergency toxicological laboratory. The utility of the method is demonstrated on two cases of human intoxication with ethylene glycol.     

Reaction of mercury(II) and xylenol orange-I Effect of the buffering media

The influence of the buffering medium on the reaction of Hg(II) with Xylenol Orange has been studied. Amine-type compounds are complexed by Hg(II)/Xylenol Orange with a sharp hyperchromic effect on the reagent itself, at 590 nm, but complex formation of Hg(II)/Xylenol Orange in non-amine-type buffer, such as citric acid-phosphate, gives a hypochromic effect on Xylenol Orange at 580 nm. Hg(II) is determined at pH 7.5 in two ranges of concentration, 2-9 ppm in citrate buffer, measured at 580 nm ( = 2.50 x 10(4)), and 6-11 ppm in hexamine buffer, at 590 nm ( = 4.18 x 10(4)).     

Neue stellungsisomere reineckesalzähnliche Verbindungen mit Toluidinen

Zusammenfassung Es wurden eine Reihe von Substitutionsreaktionen mit entwässertem K₃[Cr(NCS)₆] und aromatischen Aminen, ohne Verwendung von Lösungsmitteln, durchgeführt. Es wurde beobachtet, da die sehr schwachen Basen mit p_K-Werten 14–16, wie die isomeren Mono- und Dinitro-aniline, die Anthranil- und Sulfanilsäuren, für diese Substitutionsreaktionen ungeeignet sind. Die Alkyl-anilinderivate, wie daso-, m- undp-Toluidin (p_K=10–11) bilden dagegen leicht reineckesalzähnliche Verbindungen: Amin· H[Cr(Toluidin)₂(NCS)₄]. Die Zusammensetzung der neuen Komplexanionen wurde bei einer Reihe von doppelten Umsetzungsreaktionen mit den Chlorhydraten einiger heterocyclischen Aminen festgestellt.Für die Klärung einiger Strukturfragen wurden spektrophotometrische Untersuchungen im UV und IR durchgeführt und die thermische Stabilität bzw. der Mechanismus des Pyrolysenvorganges auf thermogravimetrischem Wege verfolgt.

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Substitution reactions of anhydrous K₃[Cr(NCS)₆] with aromatic amines without applying of solvents were studied.It was observed, that the very weak bases (pK-values 14–16, e.g. isomeric mono- and dinitro-anilines, the anthranilic and sulfanilic acids) are unsuitable for substitution reactions. The alkylaniline derivates e.g.o-, m- andp-toluidine (pK=10–11) form easily reineckesalt analogous compounds: Amin· ·H[Cr(toluidine)₂(NCS)₄]·The formula of the 3 new complex anions: [Cr(toluidine)₂ (NCS)₄]- was established by preparative methods, with a series of double decomposition reactions, using chlorohydrates of some heterocyclic amines for this purpose. From spectroscopical investigations (UV and IR) some structural problems are resolved and discussed.The thermal stability and the mechanism of pyrolysis of these salts was studied by thermogravimetric analysis.

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Liquid chromatographic retention behaviour and separation of promethazine and isopromethazine on a β-cyclodextrin bonded-phase column

A liquid chromatographic method for the separation of promethazine (PR) and its positional isomer isopromethazine (IPR) is described.PR is an N-substituted phenothiazine with the actions and the uses of the antihistamines (H1-receptor antagonists). IPR is an impurity in the pharmaceutical preparations of PR and must be controlled at a level below 1%. The liquid chromatographic behaviour of PR and IPR on a hydrolytically stable β-cyclodextrin (β-CD) column with respect to mobile phase composition, pH, ionic strength and the nature of the organic modifier was also investigated. Based on the results, conditions were chosen for the isocratic separation of the two isomers. The proposed separation method is simple and rapid and permits the simultaneous determination of PR and IPR. The separation selectivity of a cyclodextrin bonded-phase column was examined. Special attention was devoted to modelling the inclusion complexes of PR and IPR with β-CD in order to predict their optimum orientation within the β-CD cavity.     

Retention of85Sr and147Pm on insoluble hydroxides and phosphates prepared by the sol-gel procedure

Retention of strontium and promethium on hydroxides (hydrated oxides) and phosphates of iron and chromium prepared by the sol-gel method was studied. The sorption was determined under static conditions depending on the pH of the solution. The sorption isotherms and retention were investigated under dynamic conditions.     

Intramolecular "Aryl-metal chelate ring" pi,pi-interactions as structural evidence for metalloaromaticity in (aromatic alpha,alpha'-diimine)-copper(II) chelates: molecular and crystal structure of aqua(1,10-phenanthroline)(2-benzylmalonato)copper(II) three-hydrate

By reaction of Cu(2)CO(3)(OH)(2), 2-benzylmalonic acid (H(2)Bzmal), and 1,10-phenanthroline (phen), [Cu(Bzmal)(phen)(H(2)O)] x 3H(2)O (compound 1) has been obtained and characterized by thermal, spectral, magnetic, and X-ray diffraction methods. The molecular structure of 1 is remarkably similar to that of [Cu(Bzmal)(bipy)(H(2)O)] x 2H(2)O (compound 2, bipy = 2,2'-bipyridine). In both complexes, the aryl(Bzmal) ring produces an unexpected pi,pi-stacking interaction with the Cu(II)-(aromatic alpha,alpha'-diimine) chelate ring, at an average distance d(pi)(-)(pi) of 3.40 A, involving roughly parallel and smoothly slipped rings. This insight is discussed as new structural evidence for metalloaromaticity of Cu(II)-(aromatic alpha,alpha'-diimine) chelate rings. Interestingly, 1 recognizes itself by a weak intermolecular pi,pi-stacking interaction between aryl(Bzmal) ligands to give pairs of complex molecules. In contrast, there is an intermolecular pyridyl-pyridyl pi,pi-stacking interaction also forming pairs of complex molecules in 2.     

Automation of the gas analysis of14C-labelled compounds utilizing a piston-type counter tube

In this paper an automatic apparatus designed for the radioactivity measurement of¹⁴C-labelled organic compounds in the gaseous phase is described. The labelled organic compounds are combusted in a mixture of argon and oxygen. After combustion the oxygen content of the gas is eliminated by passing it through a copper packing. The water and heteroelements present are also removed and the radioactive carbon dioxide gas is swept by argon carrier gas into a piston-type counter tube. In the counter tube the piston forming a dividing wall moves forward in accordance with the rate of combustion and sweeping, and thus sucks the gases leaving the combustion tube into the effective tube volume. The anode wire is carried by a reel located in the piston and a spring device ensures its stretched state. At the end of the sweeping period methane is fed into the counter tube and the activity of the argon—methane—carbon dioxide mixture is measured in the limited proportional region. Manual and automatic operation is possible. The piston-type counter tube provides possibility for strandardization by means of extrapolation and for measurement of absolute activities.