Rearrangement of 5-trimethylsilylthebaine on treatment with L-selectride: an efficient synthesis of (+)-bractazonine

Treatment of 5-trimethylsilylthebaine with L-Selectride gave rise to a rearrangement to 10-trimethylsilylbractazonine through migration of the phenyl group, whereas treatment of thebaine with strong Lewis acids is known to lead to a similar rearrangement through migration of the alkyl bridge to give, after reduction, (+)-neodihydrothebaine. It is suggested that the rearrangement of the alkyl group of thebaine is favored due to the formation of a tertiary benzylic cation. However, for 5-trimethylsilylthebaine, the lithium ion of L-Selectride acts as the Lewis acid and the beta-silyl effect dominates in the stabilization of any positive charge. This rearrangement provides a clear example of the greater relative migratory aptitude of phenyl groups over alkyl groups, and provides an efficient synthesis of (+)-bractazonine from thebaine.     

,-Difluoroketone inhibitors of HMG CoA reductase

The rationale for a new class of HMG CoA reductase inhibitors, represented by ,ga-difluoroketones 3 and 4, is described. The syntheses of 3, 4, and their nonfluorinated analogue 5 are presented.     

über die Theorien des osmotischen Druckes

Zusammenfassung Vier Einw?nde gegen die Druck-Gleichgewichts-Theorie des osmotischen Drucks werden diskutiert. Drei Anschauungen über den Zustand des L?sungsmittels beim Durchgang durch die Membran werden diskutiert und jede für bestimmte Osmosef?lle als m?glich erkannt. Es wird gezeigt, da\ jede dieserTheorien sich mit der Druck-Gleichgewichts-Theorie in Einklang befindet und da\ diese als ein Faktor bei der kinetischen Deutung des osmotischen Drucks unentbehrlich ist. übersetzt von H. Kauffmann (Leipzig).     

Experimental study of the time-dependent rate of K → πππ

The time-dependence of the decay rate of initially pure K⁰ into the final state (π⁺π⁻π⁰) has been studied in search for the decay k_S⁰→π⁺π⁻π⁰. No evidence is found in a sample of 384 observed events. The ratio of the CP -violating K_S⁰ amplitude and the K_L⁰ amplitude is η₊₋₀ = (0.13_−0.20^+0.17) + i(0.17_−0.26^+0.27); the ratio of the CP-conserving K_S⁰ amplitude and the K_L⁰ amplitude is < 0.4. The energy dependence of the K⁰→π⁺π⁻π⁰ matrix element is found to be a₊₋₀ = −0.31 ± 0.03.     

Search for pi(0)-->nu(mu)nu(mu) decays in the LSND detector

We observe a net beam excess of 8.7+/-6.3(stat)+/-2.4(syst) events, above 160 MeV, resulting from the charged-current reaction of nu(micro) and/or nu;(mu) on C and H in the LSND detector. No beam-related muon background is expected in this energy regime. Within an analysis framework of pi(0)-->nu(mu)nu;(mu), we set a direct upper limit for this branching ratio of Gamma(pi(0)-->nu(mu)nu;(mu))/Gamma(pi(0)-->all)<1.6 x 10(-6) at 90% confidence level.     

Experimental results on neutrino-electron scattering

A determination of sin² θ _w based on measurements of elastic scattering of muon-neutrinos and muon-anti-neutrinos on atomic electrons is described. These purely leptonic processes were studied using the CHARM calorimeter exposed to neutrino and antineutrino wide-band beams at the CERN super proton synchrotron. A total of 83±16 neutrino-electron and 112±21 antineutrino-electron events have been detected. From the measurement of the ratio of muon-neutrino and muon-antineutrino cross-sections a value of sin² θ _w =0.211±0.037 was obtained.