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