The Structure of the Alkaloid Peduncularine. Communication no. 172 on organic natural products

The revised structure 1 is put forward for peduncularine, the main alkaloid of Aristotelia peduncularis (Labill.) HOOK. F. (Elaeocarpaceae), on the basis of its spectroscopic properties and those of its degradation products, the Hofmann base 3 and the hydrogenation product 4 . Structure 1 represents the relative configuration of the alkaloid. Peduncularine belongs to the class of indole alkaloids with a monoterpene unit as the aliphatic portion. To our knowledge it constitutes the first example in which an isopropyl group has become detached from the terpene unit and occurs as a substituent on nitrogen.     

Sensitized photo-oxidation of methylcyclohexane as a thin film on seawater by irradiation with natural sunlight

Methylcyclohexane dissolved in and forming a thin film on purified seawater with traces of anthraquinone added as triplet sensitizer was exposed to natural sunlight in a quartz flask. The water was circulated through a glass cartridge filled with Amberlite XAD-2 for the concentration of reaction products which were identified by GC/MS after elution and silica gel chromatography. They included isomeric methylcyclohexanols as the principal components, primary hydroperoxides, a tentatively identified secondary peroxide, methylcyclohexanones, and acyclic ketones. Mass spectra and mechanisms are discussed as well as possible biological consequences of the formation of these compounds.     

Adsorption enrichment of some azo dye complexes on a carbon paste electrode and its application to the determination of small concentrations of cobalt and manganese

Summary The azo dyes eriochrome black T, eriochrome blueblack R and eriochrome blueblack B and their complexes with cobalt, manganese and magnesium show adsorption enrichment on carbon paste electrodes, dependent on the composition of the electrode filling. This effect may be used for the determination of cobalt and manganese by a.c. voltammetry in the 10^–7 to 10^–6 M range. Standard deviation has been found to be ± 3.2 and ± 3.5%, respectively.

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Adsorptive Anreicherung einiger Komplexe von Azofarbstoffen an einer Kohlepasteelektrode. Anwendung zur Bestimmung geringer Konzentrationen von Kobalt und Mangan

Zusammenfassung Die Azofarbstoffe Eriochromschwarz T, Eriochromblauschwarz B und Eriochromblauschwarz R sowie ihre Komplexe mit Kobalt, Mangan und Magnesium werden adsorptiv an Kohlepasteelektroden angereichert. Die Anreicherung ist von der Zusammensetzung der Elektrodenfüllung abhängig. Anwendungen zur wechselstromvoltammetrischen Bestimmung von Kobalt und Mangan im 10^–7 bis 10^–6 M Bereich werden beschrieben. Die Standardabweichung liegt bei ± 3,2 bzw. ± 3,5%.

Die Untersuchungen wurden in dankenswerter Weise durch Mittel der Deutschen Forschungsgemeinschaft und des Verbandes der chemischen Industrie unterstützt.     

Self-assembly of tetrahedral and trigonal antiprismatic clusters [Fe4(L4)4] and [Fe6(L5)6] on the basis of trigonal tris-bidentate chelators

In a one-pot reaction, the tetranuclear iron chelate complex [Fe4(L4)4] 6 was generated from benzene-1,3,5-tricarboxylic acid trichloride (4), bis-tert-butyl malonate (5a), methyllithium, and iron(II) dichloride under aerobic conditions. Alternatively, hexanuclear iron chelate complex [Fe(L5)6] 7 was formed starting from bis-para-tolyl malonate (5b) by employing identical reaction conditions to those applied for the synthesis of 6. The clusters 6 and 7 are present as racemic mixtures of homoconfigurational (delta,delta,delta,delta)/(lambda,lambda,lambda,lambda)-fac or (delta,delta,delta,delta,delta,delta)/(lambda,lambda,lambda,lambda,lambda,lambda)-fac stereoisomers. The structures of 6 and 7 were unequivocally resolved by single-crystal X-ray analyses. The all-iron(III) character of 6 and 7 was determined by M?ssbauer spectroscopy.     

Solvothermal Synthesis and Characterization of the New Iron Thioantimonates(III) [Fe(C6H18N4)]FeSbS4 and [Fe(C4H13N3)2]Fe2Sb4S10 Containing FeII and FeIII and Protein‐Analogous [2FeIII‐2S]2+ Clusters

The two new compounds [Fe(tren)]FeSbS₄ ( 1 ) (tren = tris(2‐aminoethyl)amine) and [Fe(dien)₂]Fe₂Sb₄S₁₀ ( 2 ) (dien = diethylendiamine) were prepared under solvothermal conditions and represent the first thioantimonates(III) with iron cations integrated into the anionic network. In both compounds Fe³⁺ is part of a [2Fe^III‐2S] cluster which is often found in ferredoxines. In addition, Fe²⁺ ions are present which are surrounded by the organic ligands. In ( 1 ) the Fe²⁺ ion is also part of the thioantimonate(III) network whereas in ( 2 ) the Fe²⁺ ion is isolated. In both compounds the primary SbS₃ units are interconnected into one‐dimensional chains. The mixed‐valent character of [Fe(tren)]FeSbS₄ was unambiguously determined with Mössbauer spectroscopy. Both compounds exhibit paramagnetic behaviour and for ( 1 ) a deviation from linearity is observed due to a strong zero‐field splitting. Both compounds decompose in one single step.     

Chloracylierung und Bromacylierung von Carbonylverbindungen: Eine in Vergessenheit geratene Carbonylreaktion. I. Präparative Anwendungsbreite

Chloroacylation and bromoacylation of carbonyl compounds: A forgotten carbonyl reaction. I. Scope of the reaction Aliphatic, α,β-unsaturated and aromatic aldehydes as well as aliphatic ketones react with acyl halides to (α-haloalkyl)esters. These bifunctional derivates contain two leaving groups of different reactivity. The scope of this scarcely of this scarcely known carbonyl reaction is discussed.     

Hausdorff-summability of power series II

Let H _x a regular Hausdorff method and P(w)=∑ a_k w^k a power series with positive radius of convergence. A theorem of Okada states that P(w) is summable (H _x ) for w in a certain starshaped region G(H _x ,P). We call G=G(H _x ,P) the exact region of summability for P if summability cannot hold for any w \( \in \bar G\) Okada's theorem is said to be sharp for H_x if G(H_x,P) is the exact region of summability for any P. Three items are treated: 1. Criteria for Okada's theorem to be sharp are given in terms of the distribution function X (t) and the Mellin transform \(D(z) = \int\limits_0^1 {t^z d\chi (t)} \) . 2. When is Okada's theorem sharp for product methods? 3. Special classes of functions P(w) are indicated such that G(H_x, P) is the exact region of summability for any H_x. We use the notations of “Hausdorff-Summability of Power Series I” referred as “I”.     

A note on the hilbertfunction of a one-dimensional Cohen-Macaulay ring

In this note we give examples of one-dimensional noetherian local integral domains with the property that the number of generators of the square of the maximal ideal is less than the embedding dimension. On the other hand we show that if \((R,m)\) is a local one-dimensional Cohen-Macaulay ring, then \((m^n )\) for all n such that μ \((m^n )\) < m(R). Here μ denotes the minimal number of generators of an ideal and m(R) the multiplicity of R. A similar statement was conjectured by D. Sally in [5], Our main result 2.1 generalizes Prop. 2.6. in [6].     

Summierbarkeit der geometrischen Reihe auf vorgeschriebenen Mengen

In this paper we are concerned with the summability of the geometric series by matrix methods. We prove the following theorem: Suppose M_o:={z:|z|<1}, M₁, M₂, is a collection of countably many Lebesgue measureable, disjoint sets. For k=1,2, let f_k be a prescribed function, analytic on . Then there exists a triangular matrix , such that the V-transform {_n(z)} of the geometric series has the following properties: {_n(z)} converges compactly to on M_o; for k=1,2, there are sets B_k, such that has Lebesgue-measure zero and _n(z)f_k(z) for zB_k; if there is a set B^*, such that B^*M^* has Lebesgue-measure zero and {_n(z)} diverges for zB^*.