Enantioselective reduction and deracemisation using the non-conventional yeast Pichia glucozyma in water/organic solvent biphasic systems: preparation of (S)-1,2-diaryl-2-hydroxyethanones (benzoins)

Water/organic solvent two-liquid-phase systems have been successfully applied in the synthesis of enantiomerically pure (S)-benzoin through two different methodologies catalysed by whole cells from the non-conventional yeast Pichia glucozyma: the stereoselective monoreduction of benzil and the deracemisation of benzoin. The presence of the organic solvent influences the redox systems implied in the reactions, avoiding the formation of the corresponding diols, increasing the enantioselectivity and allowing the easy isolation of the products in high yields and excellent enantiomeric excesses. The use of both strategies has been extended to the preparation of different chiral benzoin derivatives.     

In situ formation of allyl ketones via Hiyama-Nozaki reactions followed by a chromium-mediated Oppenauer oxidation

In Hiyama-Nozaki reactions of allylchromium with aldehydes the expected products are homoallylalcohols. However, oxidation products derived from these, predominantly allyl ketones, can be common side products. This can be explained by an Oppenauer-(Meerwein-Ponndorf-Verley)-type mechanism (OMPV-reaction). The amount of oxidation is strongly dependent on the substitution pattern of the reaction partners and the reaction conditions. An appropriate choice of these can lead to preferential formation of ketones instead of the alcohols. In addition to its synthetic usefulness, the oxidation-reduction equilibrium is of the utmost importance for the design of enantioselective Hiyama-Nozaki reactions because it is also a potential racemization pathway.     

Novel stereocontrolled addition of allylmetal reagents to alpha-imino esters: efficient synthesis of chiral tetrahydroquinoline derivatives

To prepare in multigram scale new antagonists of the glycine binding site associated to the NMDA receptor, an efficient distereoselective route was set up. The addition of suitable allyltin reagents to chiral N-aryl alpha-imino esters (R-(+)-tert-butyl lactate used as chiral auxiliary), gave the corresponding alpha amino acid-type derivative in high chemical yield and optical purity. This allylation reaction represents a novel example of efficient long-range stereodifferentiation process. In the last part of the synthesis, a regioselective Heck-type cyclization reaction enabled preparation of the target tetrasubstituted exocycle and trisubtituted endocycle double bond derivatives.     

Homogeneous Ziegler–Natta catalysis. II. Ethylene polymerization by IVB transition metal complexes/methyl aluminoxane catalyst systems

Homogeneous Ziegler-Natta systems for the ethylene polymerization, deriving from R₂R_2′M complexes (R = cyclopentadienyl; R′ = alkyl, aryl; M = Ti, Zr, Hf) and oligomeric oxoalane compounds, were studied. Further results concerning the methyl aluminoxane synthesis and the related chemistry are reported. On the basis of spectroscopic data a delocalized electronic structure could be inferred for these compounds. Results from polymerization experiments showed that the highest productivities are obtained only by oxoalane cocatalysts having a high degree of oligomerization. The catalytic activity of the systems under investigation was strongly affected also by changing both the σ-alkyl and the π-cyclo-pentadienyl ligands. Furthermore, it was found that in the presence of methyl aluminoxane, the homoleptic σ-alkyl derivatives of IVB transition metals, such as Zr(CH₂C₆H₅)₄, are also able to polymerize ethylene with a fairly high productivity. Active species containing Zr? O? Al bonds have been postulated.     

Enthalpie der Polymerisation von 7-Oxabicyclo[2.2.1]-heptan sowie exo- und endo-2-Methyl-7-oxabicyclo-[2.2.1]-heptan

Ohne Zusammenfassung     

A search for charmed particles originating from the interactions of 300 GeV/c protons in emulsion nuclei

The associated production of charmed particles by the interactions of 300 GeV/c protons with complex nuclei has been sought using nuclear emulsions. The failure to observe any candidates for this process among some 60,000 interactions investigated implies, provided charmed particles lifetimes are in the range 10^?12 to 10^?14 s, a cross section for their associated production by the interactions of 300 GeV/c protons with nucleons of less than 1.5 microbarns at a 90% confidence level.     

Studies on comblike polymers. X. Characterization of comblike polyesters by 13C NMR spectroscopy

The ¹³C NMR spectra of aromatic comblike polyesters obtained from 1,2-icosanediol and isomeric phthalic acids are reported and discussed. The analysis shows that the most informative spectral regions are those of the carbonyl and quaternary carbon resonances, whose peak multiplicities have been interpreted in terms of dyad and triad sequences. The results indicate that the extent of structural characterization possible for the polymers examined is dependent on the type of isomerism of the aromatic acid involved.     

The effect of a nonlinear temperature dependent Prandtl-number on heat transfer of fully developed flow of liquids in a straight tube

If Nu_o is the Nusselt Number for a temperature-independent Prandtl number Pr, and Nu the Nusselt number for a temperature dependent Prandtl number, it is usual to define the correction factor Nu/Nu_o=C. A correction factor which has been defined in this form has, up to now, only been expressed as a function of two characteristic Pr numbers. Thus it was simply assumed that the Pr number was a linear function of the temperature. Fluids with very large Pr numbers show a (T;Pr) relationship which deviates considerably from a linear one. This leads to a very large difference (up to 70%) between the calculated and the measured values of the Nusselt number. In the following study we shall determine a so-called curvature parameter of the (T;Pr) curve and obtain a semi-empirical formula for C. This formula has a deviation from the actual relationship many times smaller than that of the formulae for a linear (T;Pr) relationship.

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Zusammenfassung Ist Nu_o die Nusseltzahl bei temperaturunabhangiger und Nu die Nusseltzahl bei temperaturabhangiger Prandtlzahl Pr, so ist es üblich, mit Nu/Nu_o=C den Korrekturfaktor zu bezeichnen. Ein in dieser Form definierter Faktor C ist bisher als Funktion nur zweier charakteristischer Pr-Zahlen ausgedrückt worden. Es wurde somit nur eine lineare Abhängigkeit von der Pr-Zahl von der Temperatur T vorausgesetzt. Flüssigkeiten mit großen Pr-Zahlen weisen eine (T;Pr)-Charakteristik auf, die sehr stark von der linearen abweicht. Sehr große Abweichungen (bis — 70%) der gerechneten von den gemessenen Nu-Zahlen sind eine Folge davon. In vorliegender Arbeit bilden wir mit einer dritten charakteristischen Pr-Zahl einen sogenannten Krümmungsparameter der Kurve (T;Pr) und leiten eine semiempirische Formel für C ab, die um ein großes Vielfaches kleinere Fehler aufweist, als die Formeln für den linearen (T;Pr)-Verlauf.

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Nomenclature

Material constants c_p specific heat at constant pressure [J/kgK] - k heat conductivity [W/mK] - density [kg/m³] - a temperature diffusivity, a=k/c_p [m²/s] - dynamic viscosity [Ns/m²] - kinematic viscosity [m²/s] Fluid dynamics D inner diameter of the tube [m] - L length of tube [m] - w mean speed of fluid [m/s] Heat transfer h coefficient of heat transfer [W/m²K] - T absolute temperature [K] - T_b bulk temperature (corresponding to the adiabatic mixing temperature) [K] - T_w tube wall temperature [K] - T_f=(T_b+T_w)/2 film temperature [K] - T=T_b-T_w temperature forcing difference of heat transfer [K] Characteristic quantities without dimensions Re=wD/ Reynolds number - Pr=/a Prandtl number - Nu=hD/k Nusselt number - related temperature - related Prandtl number - curvature parameter of the Prandtl number Various - C=Nu_b/Nu_o correction factor according to Eq.(5) - p exponent in Eq.(6), (a), (8) and (16) Indices o corresponding to the quasi-isothermal heat transfer - b,w,f with reference to quantities, including physical properties which correspond to the temperatures T_b, T_wor T_f - Pr,k,, for quantities calculated corresponding to the Prandtl number, the thermal conductivity coefficient, the density or the dynamic viscosity - H,C for heating or cooling exp for quantities calculated from experimental data     

Estimation of dynamical invariants without embedding by recurrence plots

In this paper we show that two dynamical invariants, the second order Renyi entropy and the correlation dimension, can be estimated from recurrence plots (RPs) with arbitrary embedding dimension and delay. This fact is interesting as these quantities are even invariant if no embedding is used. This is an important advantage of RPs compared to other techniques of nonlinear data analysis. These estimates for the correlation dimension and entropy are robust and, moreover, can be obtained at a low numerical cost. We exemplify our results for the Rossler system, the funnel attractor and the Mackey-Glass system. In the last part of the paper we estimate dynamical invariants for data from some fluid dynamical experiments and confirm previous evidence for low dimensional chaos in this experimental system.