Tuning the acceptors in catalyzed cyclizations initiated by allenes. Silylstannylation/cyclization of allene-aldehydes for synthesis of polyalkylated indolizidines including 223A congeners

Starting from succinamide and 1,2-heptadiene-4-ol, a racemic allene-aldehyde substrate, 20, suitable for R(3)SiSnR'(3)-mediated cyclization was synthesized in six steps and in 21% yield. Stereoselective cyclization (relative cis configuration at the new stereogenic centers of the homoallyl alcohol generated) proceeded smoothly, giving a mixture of indolizidinols bearing five contiguous stereocenters in a combined yield of 80%. Relative configurations of each of the products were unequivocally established by a combination of 2D NMR experiments and single-crystal X-ray analysis. The major indolizidinol obtained in 32% yield was elaborated into indolizidine 5,8-epi-indolizidine 223A via a five-step reaction sequence in 32% overall yield. The second major component (24%) of the key cyclization yielded, in four steps, indolizidine 6,8-epi-223 in 14% yield. Even though revision of the initially postulated structure foiled our original synthetic plans for the natural product, indolizidine 223A, the new stereoselective cyclization strategy and several selective transformations of the indolizidine derivatives reported here may find further applications for the synthesis of highly alkylated indolizidine and other related alkaloids.     

Dielektrische Relaxation Polymerer bei Temperaturen bis 1 °K

Zusammenfassung Es werden Messungen des dielektrischen Verlustes tan im Temperaturbereich von 1 bis 80 °K und bei verschiedenen Frequenzen zwischen 10 Hz und 10 kHz an einer Reihe von Polymeren mitgeteilt.Der dielektrische Verlust sinkt im allgemeinen mit Annäherung an den absoluten Nullpunkt monoton ab. Es scheint dies anzudeuten, daß immer ein dielektrischer Untergrund, beruhend auf allgemeinen thermischen Fluktuationen, existiert, der im übrigen für Polymere mit polaren Gruppen höher liegt als für unpolar gebaute. Zu tiefsten Temperaturen hin überlagert sich diesem allgemeinen Trend oft noch ein Maximum, wenngleich bei Temperaturen bis 1 °K herab zuweilen nur erst in einer Konstanz der Verlustwinkel-Werte angedeutet. Es sieht also so aus, als ob auch noch bei tiefsten Temperaturen singuläre Relaxationsmechanismen eine Rolle spielen können. In einer Reihe von Fällen findet man weitere Relaxationsprozesse zwischen 15 und 40 °K.Soweit sich Aktivierungsgrößen aus der Auftragung der Maximallage in der Temperatur mit der Frequenz nach Abtrennung des allgemeinen Untergrundes abschätzen lassen, werden diese mit sinkender Temperaturlage immer kleiner.Die dielektrischen Verluste sind in allen Fällenextrem abhängig von der Vorgeschichte der Proben und zwar insofern, daß offensichtlich Verspannungen im Material infolge von Deformationsprozessen und anderen Behandlungen zu einer erheblichen Erhöhung der Verluste führen, sowohl des Untergrundes als der singulären Mechanismen.

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Summary Investigations of dielectric loss in the temperature range 1–80 °K and with frequencies between 10 c/sec and 10 kc/sec for diverse polymers a presented. For all polymers the dielectric loss decreases in principle monotonely with the approximation of the absolute Zero-point.Thus we suppose the existence of a common dielectric background loss depending from the thermal fluctuations in the material. Moreover this background losses are higher for substances with polar groups.At the lowest temperatures in most cases there seems to appear a loss peak. For temperatures down to 1 °K often this can be only suggested from the constancy of losses. But it seems to be a quite normal fact, that for extremely deep temperatures something as a singular relaxation mechanism may exist.Further discrete mechanisms exist for the range between 15 and 40 °K. Activation energy evaluated formally from the experimental dates in the normal manner after separation of the peaks from the background becomes smaller and smaller with decreasing temperatures.In all investigated cases the dielectric losses are very sensible to prehistory of the samples. It seems, that expecially stress, by deformation and other treatments, gives rise for an increase of loss for the background as for discrete mechanisms.

     

Gas-phase structures and mass spectra of binary pentafluorides

Most known non-radioactive pentafluorides have been examined by molecular-beam mass spectrometry and by the deflection of molecular beams in inhomogeneous electric fields. Extensive association of the vapors occurs for all but the lighter pentafluorides and the interhalogens. The interhalogen pentafluorides are strongly polar, consistent with the accepted C_4v symmetry. The transition-metal and Group V pentafluorides are all non-polar, except VF₅ and CrF₅ for which temperature-dependent polarity is observed. However, uncertainty exists as to whether these observations are applicable to monomeric pentafluorides in all cases. Mass-spectral cracking patterns are presented for all species.     

Investigation on the chemistry of berbans—VII: Synthesis of 10,11-dimethoxy(depyrrolo)raunescine stereoisomers

Acyloxy-ketone rearrangement, proceeding by the action of base, has been observed in the case of ketone 2. By the reduction of ketones 2 and 3 with sodium boron hydride, new 10, 11-dimethoxy(depyrrolo)raunescine stereoisomers (5a–7a) have been prepared. Previously known alcohols with alloberban skeleton (12,13) have been similarly converted into tetracyclic raunescine stereoisomers (8a,9) by the oxido-reductive method. The stereochemistry of these compounds has been investigated by physical (¹H NMR, IR) and by chemical methods.     

Potentiometric studies of dithiooxamide with a sulphide-selective membrane electrode

The sulphide-selective electrode is applicable to the determination of dithiooxamide by titration with silver nitrate. The effect of the alkali content of the solutions on the reaction has been studied. The reaction products are silver sulphide, oxalic acid, and nitric acid. If the alkali concentration of the solution is lower than that equivalent to the acid formed during the titration, the amount of sulphide produced by hydrolysis decreases and the equilibrium potential is established more slowly.The determination is rapid and accurate in the presence of 1 M sodium hydroxide.     

Interaction of adenine and thymine with aqueous sugar solutions

The solubility of the nucleic acid bases, adenine and thymine, in aqueous erythritol, xylose, glucose, and sucrose solutions has been studied. The solubility of adenine increases linearly with glucose and sucrose concentration, whereas with the other reagents a nonlinear increase is observed. Below 1.5M reagent concentration, the solubility of adenine increases in the order erythritol < robose, xylose < glucose < sucrose. The solubility of thymine in these solutions, on the other hand, decreases, increases, or does not change depending upon the reagent. The effect of temperature on the solubility of adenine and thymine in sugar solution indicates that the transfer of these molecules from water to sugar solution is exothermic.Presented in part at the VIIth All-India Symposium in Biophysics held at Visva Bharati University during October 1976.     

Adsorption Peculiarities of Carbon Monoxide on Iridium Electrodeposits

The transients of current and open-circuit potential observed at CO adsorption on Ir/Pt electrodes in solutions of sulfuric and hydrochloric acids are shown to adequately agree with those theoretically expected. From voltammetric curves of electrooxidation of chemisorbed CO, the values of its adsorption are estimated by making a proper double-layer correction. It is concluded that CO is preferentially adsorbed in the bridge form. During CO adsorption from sulfuric acid solutions on an electrode with a preliminarily accumulated monolayer of copper adatoms (Cu_ad), small negative current are observed and Cu_ad are displaced by 50%. To explain these results, it is assumed that CO is reduced by copper adatoms.     

Atomic Absorption Assay of Noble Metals in Ores with the Use of Sample Decomposition by Ultrasound

An atomic absorption assay of gold, silver, and palladium in various types of ores is performed with the use of ultrasound at the fire assay stage. It is shown that ultrasound can reduce the temperature and duration of fusion and increase the recovery of noble metals into the lead button.     

Organic synthesis on the microgram scale. V

Summary This paper describes a method for theg synthesis of flavone acetates in a sealed capillary tube. The reaction products are separated and purified on a thin-layer plate. The esters are then hydrolyzed on the plate and the parent flavones regenerated. A simple heating device is used which allows for observation of the reaction.

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Zusammenfassung Beschreibung der Mikrogrammsynthese von Flavonacetaten in einem verschmolzenen Kapillarröhrchen. Die Reaktionsprodukte werden auf einer Dünnschichtplatte getrennt und gereinigt. Dann verseift man die Ester auf der Platte und stellt die freien Flavone dar. Ein einfaches Heizgerät ermöglicht die Beobachtung der Reaktion.

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For part IV of this series see Mikrochim. Acta [Wien]1969, 352.     

A family of multiderivative methods for the numerical solution of the Schrödinger equation

A family of multiderivative methods with minimal phase-lag are introduced in this paper, for the numerical solution of the Schrödinger equation. The methods are called multiderivative since uses derivatives of order two, four or six. Numerical application of the new obtained methods to the Schrödinger equation shows their efficiency compared with other similar well known methods of the literature.Active Member of the European Academy of Sciences and Arts