Solvents for ultraviolet spectrophotometry

Mathematical relations are presented showing the effect of light absorption by the solvent on the absorption measurements. A simple modification in the silica-gel adsorption method of purifying isooctane is described that greatly improves the transmittance in the 2000 Å region. A procedure of purifying dioxan is also included.     

The use of Hückel theory charge densities and localization energies for the prediction of kinetic and thermodynamic factors involved in an assumed model for the hydrohalogenation of 1,3-butadiene,isoprene and chloroprene

It is assumed that the first step in the hydrohalogenation of a diene under conditions such that an ionic mechanism is operative involves the formation of a linear carbonium ion via attachment of a proton to the 1-position and that the second step involves addition of the halide ion to either the 2- or 4-positions. If it is also assumed that hyperconjugation plays some non-negligible role in the carbonium ion intermediate, then it turns out that the use of Hückel theory charge densities and localization energies predict (1) that the 1,2-product is kinetically favored in the cases of butadiene and isoprene, (2) that the 1,4-product is kinetically favored in the case of chloroprene, and (3) that the 1,4-product is thermodynamically favored in all of the above systems. All of these predictions appear to be in agreement with available experimental results.

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Zusammenfassung Bei der Addition von Halogenwasserstoffen an die hier untersuchten Diene wird im Reaktions-ablauf ein lineares Carbeniumion angenommen. Das Proton wird in 1-Stellung addiert und in einem zweiten Schritt wird das Halogenion in 2- oder 4-Stellung angelagert. Weiter wird angenommen, daß Hyperkonjugation beim intermediären Carbeniumion eine Rolle spielt. Aus den mit der Hückel-theorie ermittelten Ladungsverteilungen und Lokalisierungsenergien läßt sich dann voraussagen, daß (1) das 1,2-Produkt bei Butadien und Isopren, (2) das 1,4-Produkt bei Chloropren kinetisch und (3) das 1,4-Produkt in allen Fällen thermodynamisch bevorzugt ist. Diese Voraussagen scheinen mit den bekannten experimentellen Resultaten übereinzustimmen.

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Résumé On admet que l'hydrohalogénation d'un diène dans des conditions où prévaut un mécanisme ionique comporte comme première étape la formation d'un ion carbonium linéaire par addition d'un proton à la position 1 et comme seconde étape l'addition de l'ion halogène à l'une des positions 2 ou 4. Si l'on admet par ailleurs que l'hyperconjuguaison joue un rôle non négligeable dans l'intermédiaire carbonium, l'emploi de la théorie de Hückel permet de prédire à l'aide des densités de charge et des énergies de localisation (1) que le produit 1,2 est favorable du point de vue cinétique dans les cas du butadiène et de l'isoprène (2) que le produit 1,4 est favorable du point de vue cinétique dans le cas du chloroprène et (3) que le produit 1,4 est favorable du point de vue thermodynamique dans tous ces systèmes. Toutes ces prédictions sont apparemment en accord avec les résultats expérimentaux disponibles.

     

Magnetic properties of copper(II) complexes with some hydrazones of substituted salicylaldehydes

A series of novel mono-and binuclear copper(II) complexes with substituted salicylaldehyde acylhydrazones H₂L of the formula CuL · xH2O (x = 0 and 1) and [Cu(HL)](ClO₄)(CH₃OH) were synthesized. The isolated dimeric complexes of copper acetate were found to exist as isomers with different bridging atoms. In dimers showing a superexchange between the paramagnetic centers through bridging phenoxide O atoms, the antiferromagnetic exchange couplings were much stronger than those in complexes with bridging O atoms of the a-oxyazine fragment.     

Thermal analysis of diazo pigments

The differential-thermal and thermogravimetric analysis of eight derivatives of 1,4-bis-(8′-hydroxy-3′,6′-disulpho-1′-naphthyl)-benzenediamide showed that these compounds have a marked exothermic effect, with maxima in the temperature range 290–340°C. The 4-nitroaniline derivative was found to undergo a blast-like decomposition in the temperature interval 285–295°C, reflected by large steps in the TG curves. The thermal analysis of diazo pigments permits determination of their applicability at higher temperatures.     

Studies on the determination of diacetyl guanfubase A concentration in rabbit plasma and pharmacokinetics

A gas chromatographic method for monitoring diacetyl guanfubase A in plasma is described. The procedure involved a single solvent extraction of drug from rabbit plasma into ethyl acetate with guanfubase A as an internal standard. The extract was analyzed subsequently on a gas chromatograph equipped with a hydrogen flame ionization detector. The recovery was 86.43% +/- 6.90% (+/- SD); the RSD of within-day and between-day was 2.81%-5.26% and 5.22%-8.24%, respectively; the regression line was linear over the concentration range of 25-200 micrograms/mL, the limit of detection was 10 micrograms/mL. No endogeneous interference was found in chromatograms of the biological samples. This method was applied to the pharmacokinetic study of diacetyl guanfubase A in rabbits.     

Synthesis and reactivity of dimeric Ar'TlTlAr' and trimeric (Ar"T1)3 (Ar', Ar" = bulky terphenyl group) thallium(I) derivatives: Tl(I)-Tl(I) bonding in species ligated by monodentate ligands

The synthesis and characterization of three new organothallium(I) compounds are reported. Reaction of (Ar'Li)(2) (Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2)) and Ar"Li (Ar" = C(6)H(3)-2,6-(C(6)H(3)-2,6-Me(2))(2)) with TlCl in Et(2)O afforded (Ar'Tl)(2) (1) and (Ar' 'Tl)(3) (2). The "dithallene" 1 is the heaviest group 13 dimetallene and features a planar, trans-bent structure with Ar'Tl-Tl = 119.74(14) degrees and Tl-Tl = 3.0936(8) A. Compound 2 is the first structurally characterized neutral, three-membered ring species of formula c-(MR)(3) (M = Al-Tl; R = organo group). The Tl(3) ring has Tl-Tl distances in the range ca. 3.21-3.37 A as well as pyramidal Tl geometries. The Tl-Tl bonds in 1 and 2 are outside the range (2.88-2.97 A) of Tl-Tl single bonds in R(2)TlTlR(2) compounds. The weak Tl-Tl bonding in 1 and 2 leads to their dissociation into Ar'Tl and Ar' 'Tl monomers in hexane. The Ar'Tl monomer behaves as a Lewis base and readily forms a 1:1 donor-acceptor complex with B(C(6)F(5))(3) to give Ar'TlB(C(6)F(5))(3), 3. Adduct 3 features an almost linear thallium C(ipso)-Tl-B angle of 174.358(7) degrees and a Tl-B distance of 2.311(2) A, which indicates strong association. Treatment of 1 with a variety of reagents resulted in no reactions. The lower reactivity of 1 is in accord with the reluctance of Tl(I) to undergo oxidation to Tl(III) due to the unreactive character of the 6s(2) electrons.     

Structure analytical methods for quantitative reference applications

The analytical methods mass spectrometry, UV/Vis, IR, Raman, Fluorometry, XRD, Mössbauer, and NMR used to elucidate chemical structure are evaluated regarding their capabilities to be used as primary analytical techniques in quantitative measurements, considering the criteria in the CCQM definition of primary methods. This includes a review of the respective measurement equations, the evaluation of the measurement uncertainty, and a discussion of evidence for the “highest metrological level”, as obtained from intercomparisons in contest with other methods. It is shown that only few methods fulfill the CCQM criteria. Quantitative NMR spectroscopy is one of them and may be considered as a potential primary method as recommended by CCQM because of being free of empirical factors in the uncertainty budget.     

Mass spectrometric study of the pyrolysis of perfluorinated compounds of composition C6F12-C9F20, containing perfluoroisopropyl groups

The primary and final products arising from the pyrolysis of perfluoro-2,4-dimethyl-3-ethylpentane, perfluoro-3-isopropyl-4-methyl-2-pentene, perfluoro-2-methyl-3-isopropyl-2-pentene, perfluoro-2,4-dimethyl-3-heptene, and perfluoro-4-methyl-2-pentene have been studied using low-energy mass spectrometry and chromatography-mass spectrometry. Thermal decomposition of hexafluoropropene oligomers, containing perfluoroisopropyl groups attached to a double bond, occurs via loss of a radical pair to form perfluorodienes, as well as via abstraction of a hexafluoropropene molecule from the iso-C₃F₇ group. A correlation between the principal fragmentation pathway observed under electron impact and the primary process in the main thermolysis pathway was detected only in the case of perfluoro-4-methyl-2-pentene and perfluoro-2,4-dimethyl-3-heptene, which are capable of cleavage of^.CF₃ and^.C₂F₅ radicals, respectively, to give a single possible allyl radical structure.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1037–1041, May, 1990.     

Structures de l'odyendane et l'odyendene deux nouveaux quassinoides d'odyendea gabonensis (pierre) engl. Simaroubacees.

From the trunk bark of Odyendea gabonensis (Pierre) Engl. Simaroubaceae, two-new quassinoids have been isolated : Odyendane and Odyendene. Their structures were established from spectral data and X-Ray diffraction analysis.     

Photometric flow-injection measurements with flow-cell employing light emitting diodes

Summary The flow-injection cell based on a light emitting diode and phototransistor as light source and detector respectively has been constructed and tested. As control procedures bismuth determination with Xylenol Orange and phosphate determination with molybdate and ascorbic acid were described. The working curve may be prepared as a function of absorbance or directly of photocurrent intensity.

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Photometrische Messungen der Durchfluinjektion in einer Durchfluß-küvette mit Hilfe lichtgebender Dioden

Zusammenfassung Eine Durchfluß-Injektionsküvette in Verbindung mit einer lichtgebenden Diode und einem Phototransistor als Lichtquelle bzw. als Detektor wurden hergestellt und geprüft. Zur Prüfung wurden die Wismuthbestimmung mit Xylenolorange sowie die Phosphatbestimmung mit Molybdat und Askorbinsäure verwendet. Die Standardkurve kann als Funktion der Absorbanz oder als Funktion der Lichtstromstärke konstruiert werden.