Palladium catalyzed insertion of carbon monoxide into benzyl-tetrahydroisoquinolines : A new synthesis of berbine alkaloids

A new total synthesis of the berbine alkaloid ring system has been achieved. Palladium catalyzed insertion of carbon monoxide into the 1 - (2 - bromobenzyl) - substituted - 1,2,3,4 - tetrahydroisoquinolines (1a–1d) by the use of catalytic amounts of palladium diacetate and triphenylphosphine in the presence of tri-n-butylamine afforded the berbin-8-ones (2a–2d) which, on reduction with lithium aluminium hydride gave the berbines (±)-berbine 3a, (±)2,3-dimethoxyberbine 3b, (±)-xylopinine 3c and (±)-pseudoepitetrahydroberbine 3d.     

Information theory in analytical chemistry: basic terms, definitions and interpretations. Arbeitskreis "Automation in der Analyse"

The most important terms in information theory (information, character, code, message and signal) are defined and interpreted with reference to automation in analytical chemistry. The aim of this communication and the earlier one dealing with systems theory, is to facilitate communication and understanding between all specialists working on or with automated systems for analysis.     

An electron-diffraction study of the molecular structure of gaseous perbromyl fluoride and calculation of its force field and vibrational amplitudes

The molecular structure of FBrO₃ has been studied by gas-phase electron diffraction. Least-squares refinements of the molecular geometry using fixed spectroscopic amplitudes revealed two geometrical minima. Initially, the amplitudes employed were derived from diagonal force fields obtained by spectroscopic least-squares refinements to fit observed and calculated wave numbers; for each geometry there are two spectroscopic minima. In the lowest geometrical minimum the wave number agreement is poor, however, the introduction of the ∠OBrO/∠FBrO interaction force constant removed the discrepancies; the resulting force field is F(Br-O) = 6.92 ± 0.02 mdyn Å^?1F(Br-F) = 3.22 ± 0.03 mdyn Å^?1, F(∠OBrO) = 1.06 ± 0.02 mdyn Å, F(∠FBrO) = 0.81 ± 0.03 mdyn Å, F(∠OBrO/∠FBrO) = ?0.19 ± 0.02 mdyn Å. In the corresponding geometrical minimum r_g(Br-O) = 1.582 ± 0.001 Å, r_g(Br-F) = 1.708 ± 0.003 Å, r_α(∠OBrO) = 114.9 ± 0.3°, r_α(∠FBrO) = 103.3 ± 0.3°. Perpendicular amplitude correction coefficients, calculated for each force field employed, were used throughout to relate the interatomic distances through the r_α-structure. The geometries of the r_α^o- and r_e-structures are estimated.     

Darstellung und spektroskopische Eigenschaften von Nitridophthalocyaninatorhenium(V)

Preparation and Spectroscopical Properties of Nitridophthalocyaninatorhenium(V) Nitridophthalocyaninatorhenium(V) ([ReNPc^2?]) is prepared by the reaction of dirheniumheptoxide with ammoniumiodide in molten 1,2-dicyano-benzene. The diamagnetic complex is chemically und thermically extremely stable. In the Uv-vis spectra the typical π-π*-transitions of the Pc^2? ligand are observed. Extra bands in the solid state spectrum are due to strong excitonic coupling of ca. 2.8 kK. In the resonance Raman spectra the intensity of the Re≡N stretching vibration (v(Re≡N)) at 969 cm^?1 is selectively enhanced by laser excitations above 19.0 kK. v(Re≡N) is a dominant m.i.r. absorption at 976 cm^?1.     

Differential spectrophotometric determination of micro amounts of metal ions in mixtures

A differential spectrophotometric method is described for the simultaneous determinations of iron and molybdenum, iron and titanium, iron and uranium, molybdenum and titanium, and molybdenum and uranium in mixtures, in a single solution at room temperature. The general method consists in treating the mixture with 5 ml of 1 M sodium acetate and 1 ml of 1% pyrocatechol in 25-ml volumetric flasks. The optical density of color of mixed complexes is determined at the corresponding pair of wavelengths suggested. From the optical density and molar extinction coefficient, the concentration of each ion in mixtures has been calculated. By this procedure, the metal ions can be determined even if they differ by large ratios. Procedures have been extended for the analysis of mixtures containing iron, molybdenum, and titanium (or uranium). These procedures can be applied for the analysis of any type of materials, like minerals, rocks, ores, alloys, steels and refractory materials. Spectra of each complex and their Beer's law were studied in detail. Experiments were also made to show that the calculated and observed optical density of mixture complexes is the same, thereby the additive of optical density of mixtures at each pair of wavelengths suggested for individual determinations of ions have been verified.     

Metallorganische Lewis-Säuren. XLII. Carbonyl- und Nitrosyl-Komplexe von Mangan und Rhenium mit schwach koordinierten Anionen (Ph3P)2(ON)2MnX, (Ph3P)n(OC)5–nMX (M = Mn,Re; n = 1, 2; X = FBF3, OSO2CF3, OSO2F,OCORf)

Organometallic Lewis Acids. XLII. Carbonyl- and Nitrosyl Complexes of Manganese and Rhenium of Weakly Coordinated Anions (Ph₃P)₂(ON)₂MnX, (Ph₃P)_n(OC)_5–nMX (M = Mn, Re; n = 1, 2; X = FBF₃, OSO₂CF₃, OSO₂F, OCOR_f) The complexes (Ph₃P)₂(ON)₂MnX (X = FBF₃, OSO₂CF₃, OSO₂F, OCOCF₃, OCOC₃F₇) and (Ph₃P)_n(OC)_5–nMX (M = Mn, Re; n = 1, 2; X = FBF₃, OSO₂CF₃) have been obtained by reaction of (Ph₃P)₂(ON)₂MnH and (Ph₃P)_n(OC)_5–nMeMe with the corresponding acids HX or from (Ph₃P)_n(OC)_5–nReBr (n = 1, 2) with silver salts AgX, respectively. The compounds have been characterized by their IR and partially by ¹⁹F-NMR data. An efficient method for the preparation of the hydride (Ph₃P)₂(ON)₂MnH is reported.     

Anreicherung und Nachweis polycyclischer aromatischer Kohlenwasserstoffe in Wasser

Zusammenfassung Ein einfaches und schnelles Adsorptionsverfahren zur Anreicherung von polycyclischen aromatischen Kohlenwasserstoffen (=PAK) wird angegeben: nach einer Magnesiumhydroxidfällung in der Wasserprobe wird der Niederschlag abzentrifugiert und durch Zugabe von Ammoniumchlorid gelöst; die organischen Substanzen in dieser Lösung werden mit sehr wenig Cyclohexan extrahiert, wodurch eine Einengung des Extraktes nicht erforderlich ist. Die PAK im Extrakt werden gas-chromatographisch mit ECD-Detektion getrennt. Ein Vergleich dieser neuen Methode mit der rapid liquid extraction wird beschrieben.

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Enrichment and analysis of polycyclic aromatic hydrocarbons in water

Summary A simple and rapid adsorption method for the enrichment of polycyclic aromatic hydrocarbons (=PAH)is described: after precipitation of magnesium hydroxide in the water sample the precipitate is separated by centrifugation and then dissolved by adding ammonium chloride; the organic substances in this solution are extracted with a very small volume of cyclohexane. A concentration of the extract is not necessary. The PAH in the extract are, separated gaschromatographically using ECD detection. The new method is compared with the rapid liquid extraction method.

     

Nuclear magnetic resonance relaxation titration

Summary Quantitative determination of the concentration of paramagnetic ions in aqueous solutions is performed by NMR relaxation titration. By measurement of the nuclear spin-lattice relaxation time T ₁ or the nuclear spin-spin relaxation time T₂ redox titrations and complexometric determinations of the concentration of paramagnetic ions are possible. Also the precipitation of ions from the solution can be followed by this method. The use of a magnetic indicator in this analytical method is shown. The sensitivity of the method goes down to concentrations as low as 10^–3 M. The accuracy of NMR relaxation titration is better than 1%. A number of applications of the method are given.

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Kernmagnetische Relaxationstitration

Zusammenfassung Quantitative Bestimmungen von paramagnetischen Ionen in wäßrigen Lösungen können mit Hilfe der kernmagnetischen Relaxationstitration durchgeführt werden. Durch Messung der Kernspin-Gitter-Relaxationszeit T ₁ oder der Kernspin-Kernspin-Relaxationszeit T ₂ als Funktion der Ionenkonzentration sind Redoxtitrationen oder komplexometrische Titrationen möglich. Der quantitative Ablauf von Fällungen kann ebenfalls verfolgt werden. Die Verwendung von magnetischen Indicatoren bei der Relaxationstitration wird beschrieben. Bestimmungen von Ionenkonzentrationen bis herab zu 10^–3 M Lösungen sind z.Z. möglich. Die Methode erlaubt eine Genauigkeit der Konzentrationsbestimmung von 1% und besser. Die Anwendung der Methode wird an einer Reihe von Beispielen gezeigt.

     

Column separation and preconcentration of copper(II), lead(II) and zinc(II) from seawater

Summary The sample of seawater (51) is freed from solid particles, buffered at pH 5.6 and percolated through a column filled with ED₃A. After sample passage 15 ml 1 M hydrochloric acid solution are pumped through the column to dissolve the concentrated ions. The final measurement using flame atomic absorption is carried out in the hydrochloric acid solution. The total labour time is less than 15 min. The standard deviations (4 analyses) for the determination of Cu, Pb and Zn (in the normal concentration range of 2–6 g · l^–1) were 2–5%, 5% and 1–10%, the recoveries 100%, 102% and 104%, respectively. A concentration coefficient of 300–500 was obtained.On leave from Lisbon University, Portugal     

Beitr?ge zur automatisierten Spurenanalyse

Zusammenfassung Ein modifiziertes automatisiertes Kaltdampf-AAS-Verfahren mit einem AutoAnalyzer II^®-System wird beschrieben. Das Verfahren erlaubt sowohl die Bestimmung von anorganischem wie die von Gesamtquecksilber und erlaubt bis zu 120 Analysen/Tag. Die Anreicherung von Quecksilber als Amalgam an Silberwolle, gefolgt von rascher thermischer Zersetzung mit Hilfe einer Graphitküvette ermöglicht eine Nachweisgrenze von 0.01 ng/ml Probenlösung. Die relative Standardabweichung für homogenes Probenmaterial und das Gesamtverfahren ist 15%. Während der Analyse von Standard-Referenz-Proben wurden keine systematischen Abweichungen beobachtet. Der mittlere Gesamt-(2)fehler für eine einzelne Probe sollte daher 30% nicht überschreiten.

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Contributions to automated trace analysisIII. A sensitive automated method for the determination of mercury in biological and environmental samples

Summary A modified automated cold vapour AAS procedure using an AutoAnalyzerII^® system is described. The procedure permits the determination of inorganic as well as total mercury and enables to perform up to 120 analyses/day. The enrichment of mercury as amalgam on silver wool, followed by a fast thermal decomposition with the aid of a graphite cuvette enables a detection limit of 0.01 ng/ml sample solution. The relative standard deviation for homogeneous samples and the overall procedure is 15%. During the analysis of certified standard reference materials no systematic deviations were observed. The average total (2) error for a single sample should therefore not exceed 30%.

Wir danken Herrn Professor Dr. H. W. Nürnberg, Direktor des Instituts für Angewandte Physikalische Chemie für sein stetes Interesse am Fortgang dieser Arbeit, sowie der zentralen Glasbläserei der KFA für die sorgfältige Anfertigung der Glas-Reaktionsapparaturen, Herrn O. Schneider für technische Unterstützung beim Probenaufschluß.     

Raman and infrared spectroscopic investigation of alkyl derivatives of arsenic acid: Part VI. On the AsO-bond - calculation of force constants and vibrational energy distribution in compounds of the type RAsO3X2 And R2A

Normal coordinate analyses and force constant calculations were carried out using frequencies of infrared and Raman-spectra of the molecules and ions RAsO₃^2?, RAs(O)(OR)₂, RAs(O)(OH)₂, RAs(OH)O₂^?, RzAsO₂^?, R₂As(O)OH, and [R'₂As(OH)₂]⁺ (R = CH₃, R' = C₂H₅). Comparing bond orders of the AsO bond with those in corresponding phosphorus, selenium and sulphur compounds, we found influences of the electron deficiency effect and of bond polarity.     

An electron diffraction study of the molecular structure of gaseous allyl silane

The molecular structure of allyl silane has been studied by gas-phase electron diffraction. The experimental radial distribution curve has only four prominent peaks, resulting in serious resolution problems in the structure determination. A single conformer whose dimensions resemble those of related molecules fits the diffraction data. The torsion angle φ_siccc is102 ± 1°, measured from the conformation having Si-C and CC eclipsed.     

β-Isothiocyanatoketones: A Convenient Source of Heterocyclic Compounds

Summary. The preparation of -isothiocyanatoketones and their reactions leading to formation of pyrimidine and bicyclic, tricyclic, tetracyclic, and pentacyclic heterocyclic compounds are reviewed. A few references concerning the rearrangement of heterocyclic compounds are also included. Some of the compounds reported have shown good antiinflammatory activity.     

Application of the theory of design of experiments in examination and elimination of the matrix effect

Summary A method of experimental optimization of an analytical procedure aimed at elimination of the matrix effect is proposed which is based on the theory of design of experiments. The criterion functions Q are formulated, which are expressed by regression coefficients in the empirical mathematical model approximating the relationship between a quantity R and the concentrations of sample components. R denotes, for example, the measured signal (e.g. absorbance, emission intensity), the concentration of a component being determined read from the calibration graph, or the error of determination. The quantities Q depend, in general, on the conditions of analysis which can be expressed by the factors z ₁..., z _M (e.g., in AAS — observation height, gas flux, concentrations of the auxiliary substances in a sample, etc.). It is assumed that the extreme of a function Q corresponds to the optimum conditions of analysis. In this paper the relationship between a quantity Q and the factors z is approximated by the polynomial model. The regression coefficients in this model are estimated on the basis of the results of an experiment carried out according to the composite rotatable design. The extreme of the model is found mathematically. Various criterion functions Q are discussed. An example concerning determination of Mg and Ca in AlCl₃ reagent by AAS is presented.

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Anwendung der Theorie der Versuchsplanung zur Untersuchung und Eliminierung des MatrixeffektsBestimmung von Mg and Ca in AlCl₃ mit Hilfe der AAS

Zusammenfassung Ein auf der Theorie der Versuchsplanung beruhendes Verfahren zur experimentellen Optimierung einer analytischen Methode mit dem Ziel der Eliminierung des Matrixeffekts wird beschrieben. Die Kriteriumfunktionen Q werden formuliert, die durch Regressionskoeffizienten in einem mathematischen Modell ausgedrückt werden, das der Beziehung zwischen einem Wert R und den Konzentrationen der Bestandteile angenähert ist. Hierbei bedeutet R z. B. das gemessene Signal (Extinktion, Emissionsintensität), den von der Eichkurve abgelesenen Konzentrationswert oder den Fehler der Bestimmung. Der Wert Q hängt im allgemeinen von den Analysenbedingungen ab, die durch die Faktoren z ₁... z _M (bei der AAS zum Beispiel die Beobachtungshöhe, der Gasstrom, die Konzentration von Hilfssubstanzen usw.) ausgedrückt werden können. Es wird angenommen, daß der Extremwert einer Funktion Q den optimalen Analysenbedingungen entspricht. Die Beziehung zwischen Q und den Faktoren z wird durch ein Polynommodell angenähert. Die Regressionskoeffizienten in diesem Modell werden aufgrund von Versuchsergebnissen bestimmt. Der Extremwert des Modells wird mathematisch berechnet. Verschiedene Kriteriumfunktionen Q werden diskutiert. Als Beispiel wird die Bestimmung von Mg und Ca in AlCl₃ mit Hilfe der AAS beschrieben.

     

Thermopower composition dependence in ferrospinels

The composition dependence of thermoelectric power (Seebeck coefficient) in ferrospinels with fixed valence foreign cations has been calculated via combined small polaron and cation distribution models. Satisfactory agreement with experimental data is achieved assuming cation distribution thermodynamic constants to be independent of foreign cation concentration. Data are analyzed for a trivalent foreign cation (Al³⁺) at elevated temperature and for divalent foreign cations (Ni²⁺, Mg²⁺, Zn²⁺) at lower temperatures.     

Schwermetallbestimmung in zwei biologischen und zwei geologischen Standards mit Hilfe der Atom-Absorptions-Spektroskopie

Zusammenfassung Die Konzentrationen der Elemente Cd, Cu, Ni, Pb und Zn wurden im Internationalen Biologischen Standard (IBS) von Bowen, im NBS Standard Reference Materials 1571 (Orchard Leaves), in Kalkstein- und Tonschieferstandards mittels Atom-Absorptions-Spektroskopie untersucht. Die Pflanzenproben wurden mit Salpetersäure/Perchlorsäure und die Gesteins- bzw. Sedimentproben mit Königwasser (31 HCl/HNO₃) aufgeschlossen. Die Messungen müssen wegen der Matrixeffekte unter Einsatz des Deuterium-Untergrundkompensators (DK) durchgeführt werden. Messungen ohne DK zeigten fehlerhafte Konzentrationserhöhungen, insbesondere im Falle des Cadmiums und des Bleis. Die Verfälschung war um so größer, je kleiner der Metallgehalt in der Materie war. Die erzielten Ergebnisse der vier Standards (mit DK) zeigen eine befriedigende Übereinstimmung mit den angegebenen Gehalten.

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Determination of heavy metals in two biological and in two geological standard materials by atomic-absorption spectroscopy

Summary Concentrations of the elements Cd, Cu, Ni, Pb and Zn were investigated in the International Biological Standard (IBS) of Bowen, in the NBS Standard Reference Materials 1571 (Orchard Leaves), in Lime Stone and Clay Slate Standards by means of flame atomic-absorption spectroscopy. The elements were determined in plant samples after digestion in nitric and perchloric acids, and in geological materials (geological standards and river sediments) after digestion in a 31 mixture of hydrochloric and nitric acids. The influence on the absorbance of the matrix was tested. Considerable interferences were found in determinations of cadmium and lead, especially when the concentration of elements was very low. These interferences could be eliminated with the help of a Deuterium Background Corrector.

     

Gas-Chromatographie von Tl, Se, Te, Hg, As, Sb, Bi, Sn als Phenylverbindungen

Zusammenfassung Die Phenylverbindungen von Thallium, Selen, Tellur, Quecksilber, Arsen, Antimon, Wismut und Zinn sind zur gas-chromatographischen Analyse dieser Elemente geeignet. Sie entstehen bis auf Thalliumtriphenyl quantitativ beim Umsatz der aus saurer Lösung extrahierten Diäthyldithiocarbamidate mit magnesiumorganischen Verbindungen. Gas-chromatographisch lassen sich die Phenylverbindungen aller acht Elemente mit einer Säule unter Verwendung eines Temperaturprogramms trennen. Im Falle des Quecksilberdiphenyls konnte keine vollständige Elution erreicht werden.Vortrag anläßlich der Tagung Euroanalysis I, 28. 8.–1. 9. 1972 in Heidelberg.     

Two new β-carboline-type alkaloids from Stellaria dichotoma var.lanceolata

Two new β-carboline-type alkaloids,dichotomine K(1) and dichotomine L(2),were isolated from the roots of Chinese medicinal plant Stellaria dichotoma L.var.lanceolata Bge.Structures of 1 and 2 were determined on the basis of chemical and spectroscopic means.     

Experimental examination of the matrix effect in the flame emission spectrometry of K, Na, and Sr

Summary The interferences in the determination of K, Na and Sr by flame emission spectrometry due to different sample components have been studied according to a new methodology of investigation of the matrix effect. This methodology comprises the formulation of mathematical (polynomial) models approximating the relationship between a measured signal (e.g. emission) and the concentration of the sample components. The regression coefficients in these models are estimated on the basis of the results of measurements carried out on appropriate standard samples. Their composition results from such experimental plans as a 2ⁿ factorial, a 3ⁿ factorial and a rotatable composite design. The 3ⁿ factorial one was the basis for the formulation of high-degree polynomial models which appeared adequate in all the cases considered. Some general problems connected with the use of this methodology in flame emission spectrometry (FES) are also discussed.

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Experimentelle Untersuchung des Matrixeffektes bei der Flammenemissions-Spektrometrie von K, Na und Sr

Zusammenfassung Mit Hilfe einer neuen Untersuchungsmethodik wurden die störenden Einflüsse von Begleitsubstanzen auf die flammenphotometrische Bestimmung von K, Na und Sr untersucht. Das Verfahren besteht in der Aufstellung mathematischer (Polynom-) Modelle, die der Beziehung zwischen Meßsignal (z. B. Emission) und Konzentration des betreffenden Bestandteils angenähert sind. Die Regressionskoeffizienten in diesen Modellen wurden aufgrund von Messungen an geeigneten Standardproben berechnet. Deren Zusammensetzung ergab sich aus entsprechenden Versuchsplänen (2ⁿ- und 3ⁿ-faktoriell sowie ein Rotationsplan). Der 3ⁿ-faktorielle Plan diente als Grundlage zur Aufstellung von Polynom-Modellen höheren Grades, die allen untersuchten Fällen genügten. Einige allgemeinere Probleme in Verbindung mit der Anwendung dieser Methodik auf die Flammenphotometrie werden ebenfalls diskutiert.