Structure, formation and catalytic studies of a meso-palladioporphyrin intermediate in a Heck reaction

A meso-palladioporphyrin intermediate was isolated from a Heck reaction between an iodoporphyrin and a non-activated olefin using a Pd(PPh3)2Cl2/Et3N system; its structure was characterized by NMR, MS and X-ray crystallography. Studies on its formation indicate that the Pd(II) catalyst was reduced in situ by Et3N with the assistance of water. The catalytic activity of the intermediate was confirmed by stoichiometric and catalytic reactions using a more reactive olefin, ethyl acrylate.     

Pseudorotation-driven dynamical structure of the tropyl radical

Despite intensive studies of the neutral tropyl radical, none of its structure, energetics, and vibrational modes are still clear. This system has puzzled scientists for over a decade since one vibrational mode frequency sharply varies from imaginary number 3000i cm-1 to the real number 6000 cm-1, depending on the calculation methods employed. We find that the origin of this peculiar mode is due to the pseudorotation (omegairot) involved in the interconversion of two nearly isoenergetic Jahn-Teller configurations (elongated structure 2B1 and compressed structure 2A2 with C2v symmetry). Here, we first report that this interconversion is not via D7h or C2v symmetry configuration but via Cs symmetry (i.e., by changing the C2v axis). This interconversion barrier is found negligibly small. Thus, the two conformers are considered to be not two different structures but a dynamically identical structure with partial quantum statistical distributions on the potential energy surface. Owing to the nearly barrierless pseudorotation, the overall structure in a short time scale (less than femtosecond) would be Cs-like between 2A2 and 2B1 configurations with small fluctuation of bond distances. However, the dynamical transitions between the 2B1 and 2A2 configurations via 14 different pseudorotation pathways would make the tropyl radical have the effective D7h structure in either a nonshort time scale (greater than femtosecond) or at nonlow temperatures, which explains the high temperature electron spin resonance experiments.     

Spektrochemische Bestimmung von Spurenelementen in Eisen und Stahl

Zusammenfassung Ein zweites spektrochemisches Verfahren zur Bestimmung von Silber, Blei, Zinn, Wismut, Tellur, Arsen und Antimon in Eisen und Stahl wurde entwickelt. Auch hier wird die spektrographische Analyse nach Auflösen der Probe in Salpetersäure und Eindampfen der Lösung zur Trockne durchgeführt. Die leichtflüchtigen Elemente werden ohne Puffer durch Anwendung eines inhomogenen Magnetfeldes und einer zweckmäßigen Elektrodenform störungsfrei und mit guter Reproduzierbarkeit bestimmt. Dabei sind die unteren Bestünmungsgrenzen gleich oder niedriger als die anderer spektrochemischer Methoden, die bisher beschrieben wurden. Das Verfahren zeichnet sich durch Schnelligkeit und Einfachheit aus.

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Spectrochemical determination of trace elements in iron and steelPart II. determination of Ag, Pb, Sn, Bi, Te, As and Sb by using an inhomogeneous magnetic field

A second spectrochemical method for the determination of silver, lead, tin, bismuth, tellurium, arsenic and antimony in iron and steel has been developed. Here also the spectrographic analysis is to be carried out after dissolution of the sample in nitric acid and evaporation of the solution to dryness. Without buffer, the easily volatile elements are determined free of interferences and with good reproducibility by using an inhomogeneous magnetic field and electrodes of an appropriate form. The lower limits of determination are the same or lower than those obtained by any other spectrochemical method described. The method is characterised by rapidity and simplicity of procedure.

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Teil I: diese Z. 254, 16 (1971).     

Facile approach for diblock codendrimers by fusion between Fréchet dendrons and PAMAM dendrons

For the first time, a simple and facile approach for the synthesis of diblock codendrimers by fusion between the azide focal point functionalized Fréchet-type polyether and the propargyl focal point functionalized Tomalia-type PAMAM dendrons has been described based on click chemistry, i.e., the copper-catalyzed cycloaddition reaction between alkyne and azide.     

Macrolactonization via hydrocarbon oxidation

A novel Pd/sulfoxide-catalyzed macrolactonization reaction of linear omega-alkenoic acids is reported that proceeds via serial ligand-catalyzed allylic C-H oxidation. The scope of this macrolactonization appears to be very broad. Aryl, alkyl, and (Z)-alpha,beta-unsaturated acids are all competent nucleophiles for this reaction, with the latter undergoing macrolactonization with no olefin isomerization. High functional group compatibility is observed that includes biologically and medicinally relevant functionality such as ortho-substituted salicylate esters, bis(indoyl)maleimides, and peptides. Evidence is provided to support the hypothesis that macrolactonization proceeds via inner-sphere functionalization from a templated pi-allylPd carboxylate intermediate.     

Non-additivity for triple point numbers on the connected sum of surface-knots

Any surface-knot in 4-space can be projected into 3-space with a finite number of triple points, and its triple point number, , is defined similarly to the crossing number of a classical knot. By definition, we have for the connected sum. In this paper, we give infinitely many pairs of surface-knots for which this equality does not hold.

     

Optical weak link between two spatially separated Bose-Einstein condensates

Two spatially separate Bose-Einstein condensates were prepared in an optical double-well potential. A bidirectional coupling between the two condensates was established by two pairs of Bragg beams which continuously outcoupled atoms in opposite directions. The atomic currents induced by the optical coupling depend on the relative phase of the two condensates and on an additional controllable coupling phase. This was observed through symmetric and antisymmetric correlations between the two outcoupled atom fluxes. A Josephson optical coupling of two condensates in a ring geometry is proposed. The continuous outcoupling method was used to monitor slow relative motions of two elongated condensates and characterize the trapping potential.     

Synthesis of novel D-2'-deoxy-2'-C-difluoromethylene-4'-thiocytidine as a potential antitumor agent

[reaction: see text] 2'-Deoxy-2'-C-difluoromethylene-4'-thiocytidine (4) as a potential antitumor agent was synthesized starting from L-xylose via 2-deoxy-2-C-difluoromethylene-4-thiosugar as a key intermediate. An elimination product, 8, was always formed as the major product during removal of the protecting groups under acidic or basic conditions. However, utilizing neutral reaction conditions to remove the protecting groups afforded the desired product 4 exclusively.