A stereoconvergent synthesis of (+)-4-demethoxydaunomycin

Sharpless kinetic asymmetric epoxidation on (±)-2-(l-hydroxyethyl)-5,8-dimethoxy-3,4-dihydronaphthalene (8) followed by LAH reduction gave R-2-(S-l-hydroxyethyl)-2hydroxy-5,8-dimethoxy-1,2,3,4-tetrahydronaphthalene and the undesired antipode. The former was converted to R-(-)-2-acetyl-2 hydroxy-5,8-dimethoxy-l,2,3,4-tetrahydronapthalen[R-(-)-5],while the latter was epimerized and recycled. R-(-)-5 has been exploited for the synthesis of(+)-4-demethoxydaunomycin     

When Can Statistical Theories Be Causally Closed?

The notion of common cause closedness of a classical, Kolmogorovian probability space with respect to a causal independence relation between the random events is defined, and propositions are presented that characterize common cause closedness for specific probability spaces. It is proved in particular that no probability space with a finite number of random events can contain common causes of all the correlations it predicts; however, it is demonstrated that probability spaces even with a finite number of random events can be common cause closed with respect to a causal independence relation that is stronger than logical independence. Furthermore it is shown that infinite, atomless probability spaces are always common cause closed in the strongest possible sense. Open problems concerning common cause closedness are formulated and the results are interpreted from the perspective of Reichenbach's Common Cause Principle (RCCP).     

Inversion of Configuration at the Phosphorus Nucleophile in the Diastereoselective and Enantioselective Synthesis of P‐Stereogenic syn‐Phosphiranes from Chiral Epoxides

Nucleophilic substitution results in inversion of configuration at the electrophilic carbon center (S_N2) or racemization (S_N1). The stereochemistry of the nucleophile is rarely considered, but phosphines, which have a high barrier to pyramidal inversion, attack electrophiles with retention of configuration at P. Surprisingly, cyclization of bifunctional secondary phosphine alkyl tosylates proceeded under mild conditions with inversion of configuration at the nucleophile to yield P‐stereogenic syn‐phosphiranes. DFT studies suggested that the novel stereochemistry results from acid‐promoted tosylate dissociation to yield an intermediate phosphenium‐bridged cation, which undergoes syn‐selective cyclization.     

Thermal decomposition of mechanically activated arsenopyrite

The changes in specific surface area and structure disorder of mechanically activated arsenopyrite were investigated. The rate of nonoxidative decomposition of mechanically activated arsenopyrite was increased almost 10-times when compared with nonoxidative decomposition of a non-activated sample. An empirical linear relationship was found (r=0.996) between the rate constant of decomposition and the ratio of specific surface to transmission of the absorption band of arsenopyrite at $\bar \nu = 370 cm^{ - 1} $ . This relationship enables us to arrange the reaction 4FeAsS→4FeS+As₄ among structure-sensitive reactions.     

Kinetics and mechanism of oxidative deoximation of benzaldoxime by diperiodatocuprate(III) intert.-butanol — Water medium

Summary The kinetics of oxidation of benzaldoxime by diperiodatocuprate(III) (DPC) was studied spectrocolorimetrically at 414 nm intert.-butanol — water medium. The order in [DPC] and that in [benzaldoxime] was unity. The rate increased with increasing [OH^–] and decreasing [IO ₄ ^– ]. A suitable mechanism is proposed based on the kinetic data.

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Kinetik und Mechanismus der oxidativen Deoximierung von Benzaldoxim mit Diperjodatocuprat(III) intert.-Butanol/Wasser

Zusammenfassung Es wurde die Kinetik der Oxidation von Benzaldoxim mit Diperjodatocuprat(III) (DPC) intert.-Butanol/Wasser colorimetrisch bei 414 nm untersucht. Die Reaktionsordnung bezüglich [DPC] und [Benzaldoxim] war gleich 1. Die Reaktionsgeschwindigkeit erhöhte sich mit Zunahme der Konzentration von [OH^–] und Verminderung von [IO ₄ ^– ]. Basierend auf den kinetischen Daten wird ein passender Mechanismus vorgeschlagen.

     

Gas-phase infrared and ab initio study of the unstable CF3CNO molecule and its stable furoxan ring dimer

The unstable trifluoroacetonitrile N-oxide molecule, CF3CNO, has been generated in high yield in the gas phase from CF3BrC=NOH and studied for the first time by gas-phase mid-infrared spectroscopy. Cold trapping of this molecule followed by slow warming forms the stable ring dimer, bis(trifluoromethyl)furoxan, also investigated by gas-phase infrared spectroscopy. The spectroscopy provides an investigation into the vibrational character of the two molecules, the assignments supported by calculations of the harmonic vibrational frequencies using in the case of CF3CNO both ab initio (CCSD(T)) and density functional theory (B3LYP) and B3LYP for the ring dimer. The ground-state structures of both molecules were investigated at the B3LYP level of theory, with CF3CNO further investigated using coupled-cluster. The CCSD(T) method suggests a slightly bent (C(s)) structure for CF3CNO, while the B3LYP method (with basis sets ranging from 6-311G(d) to cc-pVTZ) suggests a close-to-linear or linear CCNO chain. The CCN bending potential in CF3CNO was explored at the CCSD(T)(fc)/cc-pVTZ level, with the results suggesting that CF3CNO exhibits strong quasi-symmetric top behavior with a barrier to linearity of 174 cm(-1). Since both isomerization and dimerization are feasible loss processes for this unstable molecule, the relative stability of CF3CNO with respect to the known cyanate (CF3OCN), isocyanate (CF3NCO), and fulminate (CF3ONC) isomers and the mechanism of the dimerization process to the ring furoxan and other isomers were studied with density functional theory.     

Influence of mechanical activation on decomposition of a chalcopyrite-pyrite mixture in an oxidizing atmosphere

The influence of the addition of pyrite and mechanical activation on an oxidative decomposition of chalcopyrite was studied. The course of the thermoanalytical curves and X-ray identification of the products showed that addition of pyrite affects mainly the endothermic processes taking place in region of low temperatures but does not significantly influence the temperature of CuSO₄ formation and its content in the products of decomposition. Changes in fine and superfine structure of chalcopyrite brought about by mechanical activation at grinding cause the complex of exothermic oxidative reactions to proceed at temperatures as much as 180 deg lower than for a non activated sample. The endothermic effect of these oxidation reactions become more marked and the proportion of CuSO₄ in the products of the oxidative decomposition increases significantly.

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Zusammenfassung Am oxidativen Zerfall von Chalkopyrit wurde der Einfluss der Zugabe von Pyrit sowie der mechanischen Aktivierung untersucht. Der Verlauf der thermoanalytischen Kurven und Röntgendiffraktionsanalyse der Produkte zeigten, dass die Zugabe von Pyrit hauptsächlich die sich bei niedrigeren Temperaturen abspielenden endothermen Prozesse beeinflusst, nicht aber die Bildungstemperatur von CuSO₄ sowie dessen Gehalt in den Zersetzungsprodukten. Durch mechanisches Aktivieren mittels Feinmahlen hervorgerufene Veränderungen in der Fein- und Superfeinstruktur lassen die Gesamtheit der exothermen oxidativen Reaktionen bei Temperaturen ablaufen, die etwa 180 Grad unterhalb derer für unaktivierte Proben liegen. Die endotherme Färbung dieser Oxidation wird eindeutiger und der Anteil von CuSO₄ in den Produkten des oxidativen Zerfalles nimmt eindeutig zu.

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Spherical bootstrap calculation ofqqq-baryon and multiquark-hadron masses

Recently a way of implementing the dualtopological unitarization program has been found, in which baryons and other multiquark hadrons are put on the sphere and appear at the same topologicalcomplexity level as ordinary \(q\bar q\) mesons. This permits one to have a lowest-order “spherical bootstrap”, within which unitarity, duality and crossing can be consistently satisfied. In the present paper we use this framework to calculate hadron masses by imposing duality on an infinite sum of ladder graphs generated from spherical unitarity. By making a certain simple dynamical approximation, we derive an explicit generic Regge-trajectory formula for any given process. If we then make certain reasonable dynamical assumptions and require simultaneous consistency for entire sets of processes, we are able to calculate the masses of all the lowest \(q\bar q,qqq,qq\bar q\bar q,qq\bar qqq,qq\bar qq\bar q\bar q\) states withq=u, d, and the Regge trajectories associated with each of them. The only arbitrary parameter is the mass of the ?, which merely serves to set the mass scale.     

Anwendung von Methylglukamin-Maßlösung bei Säuretitrationen mit Hochfrequenz-Endpunktanzeige

Zusammenfassung Die Verfasser bringen zur Bestimmung von Säuren eine neue Titersubstanz, das Methylglukamin (1-Desoxy-1-methylamino-sorbit), in Vorschlag. Methylglukamin ist eine schwache Base mit der Dissoziationskonstante 1,5 · 10^–5 und zeigt dem bisher allgemein angewandten Ammoniumhydroxyd gegenüber zahlreiche Vorteile. Unter anderem können faktorstabile Maßlösungen aus der gut wasserlöslichen festen Base durch einfache Einwaage hergestellt werden. Zur Endpunktanzeige der Titration wurde die Hochfrequenzmethode verwendet.

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Summary A new titer substance is proposed for determining acids, namely methylglucamine (1-desoxy-l-methylamino sorbitol). Methylglucamine is a weak base whose dissociation constant is 1.5 · 10^–5 and has many advantages as compared with ammonium hydroxide which has been generally used up till now. Among others, factor-stable standard solutions can be prepared by simple weighing out of the quite water-soluble solid base. The high frequency method is applied for indicating the endpoint of the titration.

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Résumé Les auteurs proposent une nouvelle substance titrimétrique, la méthylglucamine (méthylamino-1, desoxy-1 sorbitol), pour le dosage des acides. La méthylglucamine est une base faible dont la constante de dissociation est de 1,5 · 10^–5. Elle présente de nombreux avantages par rapport à l'hydroxyde d'ammonium généralement utilisé. On peut préparer des solutions étalons stables, à partir de la base solide, facilement soluble dans l'eau, par simples pesées. Pour déterminer le point équivalent du titrage, on a utilisé la haute fréquence.

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Herrn Prof. Dr. Ing.Fritz Feigl zum 70. Geburtstag gewidmet.     

Oxovanadium(IV) complexes of bromo-and methoxy substituted N1,N4-diarylidene-S-methylthiosemicarbazones

Four new oxovanadium(IV) compounds were prepared by template reaction of salicyl-, 5-bromosalicyl-and 3-methoxysalicyl-aldehyde S-methylthiosemicarbazones with 2-hydroxy-, 5-bromo-2-hydroxy-and 3-methoxy-2-hydroxy-benzaldehyde in various combinations. The compounds were isolated as stable solid compounds with general formula [VO(L)] and characterized by elemental analysis, conductivity and magnetic measurements, electronic, IR and EPR spectroscopy. The X-band EPR signals recorded from powder forms of all samples have a single asymmetric line shape and theoretical fit studies proved the presence of axial symmetry around the paramagnetic vanadium ions. The anisotropic Lande splitting factors take values of g_‖ < g_⊥ < g_e = 2.0023. Orbital energy levels for magnetic electrons were determined from theoretically well fitted Spin Hamiltonian parameters. The EPR spectra recorded from solution forms almost have isotropic character.