Nitropyrazoles

The double Vilsmeier formylation of theC-methyl group in pyrazole derivatives has been shown to occur when a nitro-group is in the adjacent position of the ring. A method for the synthesis ofC-(diformylmethyl)nitropyrazoles based on this reaction has been developed.For the previous communication, see Ref. 1; for Part 2, see Ref.2 Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1273–1276, July, 1993.     

Conformational transitions of calixphyrin derivatives monitored by temperature-dependent NMR spectroscopy. Ab initio interpretation of the spectra

Eight meso-aryl calixphyrin derivatives were synthesized and their conformational equilibria and transitions studied with temperature-dependent NMR spectroscopy. On the basis of density functional computations, several conformer species could be identified and observed changes in chemical shifts explained. In some compounds, the aryl group rotation and porphyrin ring flipping could be monitored independently, as their NMR coalescence temperatures were well-separated. Calculated relative conformer energies, transition barriers, and isotropic shieldings agree well with the experimental data. In the meso-substituted porhyrins (calixphyrins) the sp3 carbon atoms perturb their pi-electron system and significantly modify the molecular shape and the flexibility. Even when the conjugation of the pi-electron system was destroyed by the nonplanarity, far-range electronic induction effects still exist and influence chemical shielding and molecular geometry. The aryl functional groups moderately modify the structure of the calixphyrin ring and thus can be used for fine-tuning of the mechanical and chemical properties of these compounds.     

Voltammetrische Bestimmung von Coffein in Kaffee,Tee und coffeinhaltigen Getränken

Zusammenfassung Zur Bestimmung von Coffein in Erfrischungsgetränken (Cola), Kaffee und Tee wird die Differential-Pulsvoltammetrie verwendet. Bei dieser Methode wird Coffein bei pH 1,2 an einer glasartigen Kohlenstoffelektrode oxydiert und quantitativ bestimmt. Die voltammetrisch ermittelten Analysenergebnisse werden mit den Resultaten der Flüssigkeistchromatographie verglichen. Um einen weiteren Einblick in den Reaktionsverlauf zu erhalten, wurde Coffein anodisch bei pH 1,2, 2,3 und pH 6 oxydiert. Die Reaktionsprodukte wurden kathodisch durch Differential-Pulspolarographie identifiziert.

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Voltammetric determination of caffeine in coffee, tea, and soft drinks

Summary Differential pulse voltammetry is used for the determination of caffeine in soft drinks, coffee, and tea. In this method caffeine is oxidised at a glassy carbon electrode at pH 1.2 and determined quantitatively. The voltammetric results are compared with those found by HPLC. To elucidate the mechanism of the electrode processes the reaction products were produced by anodic oxidation of caffeine at pH 1.2, 2.3 und pH 6 and then identified by cathodic differential pulse polarography.

     

Theory of the two step enantiomeric purification of 1,3 dimethylallene

An application of a recently proposed [P. Kral et al., Phys. Rev. Lett. 90, 033001 (2003)] two step optical control scenario to the purification of a racemic mixture of 1,3 dimethylallene is presented. Both steps combine adiabatic and diabatic passage phenomena. In the first step, three laser pulses of mutually perpendicular linear polarizations, applied in a "cyclic adiabatic passage" scheme, are shown to be able to distinguish between the L and D enantiomers due to their difference in matter-radiation phase. In the second step, which immediately follows the first, a sequence of pulses is used to convert one enantiomer to its mirror-imaged form. This scenario, which only negligibly populates the first excited electronic state, proves extremely useful for systems such as dimethylallene, which can suffer losses from dissociation and internal conversion upon electronic excitation. We computationally observe conversion of a racemic mixture of dimethylallene to a sample containing approximately 95% of the enantiomer of choice.     

Measurement of B0-B-0 flavor oscillations in hadronic B0 decays

Flavor oscillations of neutral B mesons have been studied in e+e- annihilation data collected with the BABAR detector at center-of-mass energies near the upsilon(4S) resonance. The data sample used for this purpose consists of events in which one B0 meson is reconstructed in a hadronic decay mode, while the flavor of the recoiling B0 is determined with a tagging algorithm that exploits the correlation between the flavor of the heavy quark and the charges of its decay products. From the time development of the observed mixed and unmixed final states, we determine the B0-B-0 oscillation frequency deltamd to be 0.516+/-0.016(stat)+/-0.010(syst) ps-1.     

Measurement of B --> K*gamma branching fractions and charge asymmetries

The branching fractions of the exclusive decays B0-->K(*0)gamma and B+-->K(*+)gamma are measured from a sample of (22.74+/-0.36)x10(6) BB decays collected with the BABAR detector at the PEP-II asymmetric e(+)e(-) collider. We find B (B0-->K(*0)gamma) = [4.23+/-0.40(stat)+/-0.22(syst)]x10(-5), B(B+-->K(*+)gamma) = [3.83+/-0.62(stat)+/-0.22(syst)]x10(-5) and constrain the CP-violating charge asymmetry to be -0.170K(*)gamma)<0.082 at 90% C.L.     

Limits on the decay-rate difference of neutral B mesons and on CP, T, and CPT violation in B(0-0)B oscillations

Using events in which one of two neutral B mesons from the decay of an Upsilon(4S) meson is fully reconstructed, we determine parameters governing decay (DeltaGamma(d)/Gamma(d)), CP, and T violation (|q/p|), and CP and CPT violation (Re z,Im z). The results, obtained from an analysis of 88 x 10(6) Upsilon(4S) decays recorded by BABAR, are sgn(Re lambda(CP))DeltaGamma(d)/Gamma(d)=-0.008+/-0.037(stat)+/-0.018(syst)[-0.084,0.068],|q/p|=1.029+/-0.013(stat)+/-0.011(syst)[1.001,1.057],(Re lambda(CP)/|lambda(CP)|) Re z=0.014+/-0.035(stat)+/-0.034(syst)[-0.072,0.101],Im z=0.038+/-0.029(stat)+/-0.025(syst)[-0.028,0.104]. The values inside the square brackets indicate the 90% confidence-level intervals. These results are consistent with standard model expectations.     

Search for the radiative decays B-->rhogamma and B0-->omegagamma

A search of the exclusive radiative decays B-->rho(770)gamma and B0-->omega(782)gamma is performed on a sample of about 84x10(6) BBmacr; events collected by the BABAR detector at the SLAC PEP-II asymmetric-energy e+e- storage ring. No significant signal is seen in any of the channels. We set upper limits on the branching fractions B of B(B0-->rho(0)gamma)<1.2 x 10(-6), B(B+-->rho+gamma)<2.1 x 10(-6), and B(B0-->omegagamma)<1.0 x 10(-6) at 90% confidence level (C.L.). Using the assumption that Gamma(B-->rhogamma)=Gamma(B+-->rho(+)gamma)=2 x Gamma(B0-->rho(0)gamma), we find the combined limit B(B-->rhogamma)<1.9 x 10(-6), corresponding to B(B-->rhogamma)/B(B-->K*gamma)<0.047 at 90% C.L.     

Measurement of the inclusive charmless semileptonic branching ratio of B mesons and determination of |V ub|

We report a measurement of the inclusive charmless semileptonic branching fraction of B mesons in a sample of 89 x 10(6) (-)BB events recorded with the BABAR detector at the Upsilon(4S) resonance. Events are selected by fully reconstructing the decay of one B meson and identifying a charged lepton from the decay of the other B meson. The number of signal events is extracted from the mass distribution of the hadronic system accompanying the lepton and is used to determine the ratio of branching fractions B((-)B-->X(u)lnu;)/B((-)B-->Xlnu;)=[2.06+/-0.25(stat)+/-0.23(syst)+/-0.36(theo)]x10(-2). Using the measured branching fraction for inclusive semileptonic B decays, we find B((-)B-->X(u)lnu;)=[2.24+/-0.27(stat)+/-0.26(syst)+/-0.39(theo)]x10(-3) and derive the Cabibbo-Kobayashi-Maskawa matrix element |V(ub)|=[4.62+/-0.28(stat)+/-0.27(syst)+/-0.48(theo)]x10(-3).