CARSA,a computer-assisted system for synthesis research in industry

Computer applications in chemical industry are outlined and the CARSA system (computer-assisted research in synthesis and application) is described. This modular system consists of the three main parts: WIFODATA (data base; substance and finding documentation), QSAR (programs for quantitative structure/activity relationships) and RDSS (reaction design by synthon substitution; program package for planning of syntheses). The vital RDSS component is discussed in more detail; the underlying philosophy is explained, and examples are given from practical work. Some future steps towards a real molecular-design system are outlined.     

Mechanisms for the solvolytic decompositions of nucleoside analogues—I: Acidic hydrolysis of 2-substituted 1-(1-ethoxyethyl)benzimidazoles

A few 2-substituted 1-(1-ethoxyethyl)benzimidazoles have been prepared and the rate constants for their hydrolysis measured at various temperatures and oxonium ion concentrations. The formal kinetics followed and the effect of varying the 2-substitution on the hydrolysis rate suggest that the acid-catalyzed cleavage of these compounds involves a rapid initial protonation of the benzimidazole ring and a subsequent rate-limiting heterolysis of the protonated substrate to form a free nitrogen base and an ocarbenium ion derived from the ethoxyethyl group. The values obtained for the entropy of activation are consistent with the assumed unimolecular nature of the rate-limiting step. The effects of 2-substituents on the acidities of the protonated substrates and their heterolysis rates have been compared. The latter partial reaction has been suggested to be the subject of steric acceleration.     

Electrostatic lattice coefficients and binding energy of orthorhombic La2-x Sr x CuO4

Three valency models for orthorhombic La_2-x Sr _x CuO₄ were investigated for increasing Sr concentrationsx (0x0.21): 1. Cu²⁺Cu³⁺, 2. apex O^2–O^– and 3. in-plane O^2–O^–. All calculations were done by using structural parameters valid for the temperature range from 10 to 22 K. We thereby calculated the electrostatic interaction energy which, next to ionization potentials and electron affinities, comprises a major of the binding energyE _B of crystals. Second-order effects were accounted for by calculating the strength of ionic dipole moments induced by crystal electric fields at relevant lattice sites. Their largest strengths are comparable to the dipole moment of the water molecule. Three out of five dipoles in La_2-x Sr _x CuO₄ vanish during the transition from the orthorhombic to the tetragonal phase. The binding energy differences between the different models suggest that the system is in a state of model 1. However, the differences are very small, being in the order of 0.3 to 0.76 eV atx=0.13.     

An investigation of intermittency in proton-gold, oxygen-gold, sulphur-gold and sulphur-sulphur interactions at 200 GeV per nucleon

The intermittency phenomenon is investigated in proton-gold, oxygen-gold, sulphur-gold and sulphur-sulphur collisions at 200 GeV per nucleon. The data were taken with the NA 35 streamer chamber detector at the CERN SPS. The data samples are carefully corrected for double counting of tracks and for contamination from photon conversions, particle decays and secondary interactions. The analysis is carried out in terms of factorial moments, using a new definition, and of correlation integrals. Both methods show the presence of nonstatistical fluctuations (intermittency). The main conclusions are: The observation of the effect for pairs of hadrons with negative charges and its near absence for pairs of opposite charges is consistent with the assumption that Bose-Einstein correlations yield the dominant contribution. The intermittency effect is not proportional to (dn/dy)^–1 which would be expected in superposition models. The measured relation between the second and third factorial moment for negative hadrons indicates that genuine 3-particle correlations are small. The predictions of a Monte Carlo simulation which is based on the Lund Fritiof model with the inclusion of Bose-Einstein correlations agree with the experimental results.Deceased     

On noise reduction methods for chaotic data

Recently proposed noise reduction methods for nonlinear chaotic time sequences with additive noise are analyzed and generalized. All these methods have in common that they work iteratively, and that in each step of the iteration the noise is suppressed by requiring locally linear relations among the delay coordinates, i.e., by moving the delay vectors towards some smooth manifold. The different methods can be compared unambiguously in the case of strictly hyperbolic systems corrupted by measurement noise of infinitesimally low level. It was found that all proposed methods converge in this ideal case, but not equally fast. Different problems arise if the system is not hyperbolic, and at higher noise levels. A new scheme which seems to avoid most of these problems is proposed and tested, and seems to give the best noise reduction so far. Moreover, large improvements are possible within the new scheme and the previous schemes if their parameters are not kept fixed during the iteration, and if corrections are included which take into account the curvature of the attracting manifold. Finally, the fact that comparison with simple low-pass filters tends to overestimate the relative achievements of these nonlinear noise reduction schemes is stressed, and it is suggested that they should be compared to Wiener-type filters.     

Chemistry of λ-2H-azaphosphirene metal complexes

In this review, important aspects of λ³-2H-azaphosphirene metal complexes are discussed in relation to synthesis, physical properties and synthetic applications; ab-initio calculations on relative energies of CH₂NP isomers and of λ³-2H-azaphosphirene metal complexes (Cr, Mo, W) are also presented. Currently, there are three routes to this unsaturated three-membered ring system, which are discussed in detail: two of them use a rearrangement of metal carbene complexes, whereas the other relies on [2+1] cycloaddition reactions of electrophilic terminal phosphanediyl complexes and carbonitriles. The structural data show characteristics of a very strained heterocyclic ring system, which partially helps to understand the reactivity of this heterocycle complex in solution. The synthetic potential of λ³-2H-azaphosphirene metal complexes is illustrated by selected examples, which demonstrate their ability to serve, under very mild conditions as precursor for various new building blocks, i.e. nitrilium phosphanylide complexes, electrophilic terminal phosphanediyl complexes and phosphavinyl-nitrene complexes.     

Two unusual, competitive mechanisms for (2-ethynylphenyl)triazene cyclization: pseudocoarctate versus pericyclic reactivity

The cyclization of (2-ethynylphenyl)triazenes in ODCB at 200 degrees C gives exclusively cinnolines, whereas addition of CuCl to 1,2-dichloroethane solutions of the triazenes at 50 degrees C results in the sole formation of isoindazoles. DFT calculations and deuterium labeling studies suggest the intermediacy of a 3-dehydrocinnolinium ion, produced through a pericyclic transition state. Calculations and trapping studies strongly implicate a carbene intermediate in isoindazole formation, which proceeds through a pseudocoarctate transition state.     

Gewöhnliche lineare Differentialgleichungen zweiter Ordnung mit Distributionskoeffizient

Zusammenfassung Läßt man in der gew. lin. Dgl. zweiter Ordnung einen Distributionskoeffizient zu, der Ableitung einerL _loc ² -Funktion ist, so existieren eindeutig festlegbare, stetige Lösungen derart, daß die in der Dgl. auftretenden Produkte definiert werden können. Mit einer Regularisierung des Distr.-Koeffizienten können die Lösungen durchC -Funktionen approximiert werden. Es wird der Sturmsche Vergleichssatz verallgemeinert. Hieraus und aus den Eigenschaften der mit zwei Basislösungen gebildeten Lösungskurve folgt die Gültigkeit des Ljapunovschen Satzes über die Eigenwertverteilung der verallgemeinerten Hillschen Dgl. mit positivem Distr.-Koeffizient, falls eine zusätzliche Bedingung erfüllt ist. Die vorliegende Arbeit enthält einige Ergebnisse meiner Dissertation [6] (weitere Resultate und Details finden sich dort).     

Regge Models of Proton Diffractive Dissociation Based on Factorisation and Structure Functions

Recent results by the authors on proton diffractive dissociation (single, double and central) in the low-mass resonance region with emphasis on the LHC kinematics are reviewed and updated. Based on the previous ideas that the contribution of the inelastic proton–Pomeron vertex can be described by the proton structure function, the contribution of the inelastic Pomeron–Pomeron vertex appearing in central diffraction is now described by a Pomeron structure function.     

Chiral and water‐soluble poly(2‐oxazoline)s

We describe the synthesis and characterization of the first water‐soluble and chiral poly(2,4‐disubstituted‐2‐oxazoline)s. While poly(2,4‐dimethyl‐2‐oxazoline)s are water soluble up to 100 °C, aqueous solutions of poly(2‐ethyl‐4‐methly‐2‐oxazoline) exhibit a lower critical solution temperature. This is discussed in context with its constitutional isomers poly(2‐oxazoline)s and poly(2‐oxazine)s. Circular dichroism spectroscopy revealed strong Cotton effects, which are also responsive to temperature in aqueous solution. It is therefore hypothesized that structures, comparable to polyproline helices, are formed in aqueous solution. In contrast to polyproline, poly(2,4‐disubstituted‐2‐oxazoline)s are highly water soluble and therefore represent very interesting pseudo‐polypeptides that may be useful to develop responsive biomimetic biomaterials. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013