Biologically active compounds through catalysis: efficient synthesis of N-(heteroarylcarbonyl)-N'-(arylalkyl)piperazines

A practical route for the synthesis of new biologically active 5-HT(2 A) receptor antagonists has been developed. In only three catalytic steps, this class of central nervous system (CNS) active compounds can be synthesized efficiently with high diversity. As the initial step, an anti-Markovnikov addition of amines to styrenes provides an easy route to N-(arylalkyl)piperazines, which constitute the core structure of the active molecules. Here, base-catalyzed hydroamination reactions of styrenes with benzylated piperazine proceeded in high yield even at room temperature. After catalytic debenzylation, the free amines were successfully carbonylated with different aromatic and heteroaromatic halides and carbon monoxide to yield the desired compounds in good to excellent yields. The two key reactions, base-catalyzed hydroamination of styrenes and palladium-catalyzed aminocarbonylation of haloarenes/heterocycles, showed tolerance towards various functional groups, thereby demonstrating the potential to synthesize a wide variety of new derivatives of this promising class of pharmaceuticals.     

Synthese von 2-methylalanin-peptiden,die pH-Abhängiggkeit ihrer 13C-NMR-spektren und eine neue methode zur auswertung über CS-diagramme

The uncommon amino-acid 2-methylalanine (α-aminoisobutyric acid, Aib) was investigated by ¹³C-NMR. The chemical shifts of amino- or carboxy-protected derivatives of Aib and of protected oligopeptides are discussed with respect to neighbouring groups and amino acids. The pH-dependence of the ¹³C-NMR spectra of Aib, Aib-Ala, Ala-Aib, Aib-Ala-Aib and Aib-Ala-Aib-Ala-Aib was studied. Using these examples, a new and advantageous method is demonstrated for the first time for the evalutions of NMR titration curves, which uses so-called chemical shift diagrams (CS diagrams).     

Saturation of resonant frequency conversion processes in cadmium vapour

We have investigated two-photon resonant up conversion of 375 to 159 nm coherent radiation using the four-frequency process ₁₅₉=2₃₇₅+₁₀₄₀ in cadmium vapour, where the ir component (1040 nm) is internally generated by the 375 nm pump tuned to the Cd two-photon transition 5s ^{2 1} S ₀5s6s ¹ S ₀. Scaling laws and tuning behaviour of both the 159 and 1040 nm output power were measured up to 1×10⁸ W cm^–2 pump intensity and 2×10¹⁷ cm^–3 Cd number density. The results are compared to numerical calculations based on semiclassical theory in a stationary perturbation approximation up to third order. Here, in accordance with experimental results, the ir component was assumed to originate from a superposition of stimulated emission and parametric generation. The observed saturation effects turned out to be mainly due to population changes of the atomic levels involved and are qualitatively reproduced by calculations. Discrepancies with respect to absolute output levels are discussed in terms of the approximations in the theoretical formalism.     

Der Transport von VO2 mit Cl2 und HCl + Cl2 und der Einfluß des O2-Bodenkörpergleichgewichtsdruckes auf den Transport

The Chemical Transport of VO₂ with Cl₂ and HCl + Cl₂ and the Influence of the O₂-Coexistence Equilibrium Pressure on the Transport Behaviour The transport behaviour of VO₂ with Cl₂, HCl, and Cl₂ was calculated and compared with the experimental results. VO₂ with the upper phase boundary transports with HCl and HCl + Cl₂ from the colder to the hotter zone, VO₂ of the lower phase boundary does not transport with HCl. The composition of the deposited VO₂ is near the upper boundary oxygen richer than in the start space. VO₂ does not transport with Cl₂.     

Improvements of a combined size exclusion chromatography and solid phase extraction approach for the clean-up of marine sediment samples for trace analysis of pesticides

 Two methods based on gel permeation chromatography (GPC) [size exclusion chromatography] for the analysis of traces (ng/kg) of nitrogen and phosphorus containing pesticides (like triazines or phosphothionates) from marine sediment samples are compared: A macro GPC with Biobeads SX-3 and a chromatography on a high-performance (HP-GPC) column with UV-detection. Results for eight triazine herbicides, two triazine metabolites, the phenylurea derivative linuron, two acetanilides and two organophosphorus compounds are given. Concentrations obtained with the HP-GPC are compared with those obtained with a macro GPC approach in an earlier study. Received: 4 October 1996/Revised: 20 December 1996/Accepted: 24 December 1996     

Zur Charakterisierung einer Klasse von Hyperbelstrukturen

A characterisation of those (B^*G)-Geometries (in the sense of Benz) is given, which can be constructed with the help of nearfields F, char F 2, in which the multiplicative group F^*(·) has a subgroup A with index [F^*:A]=2.

---

---

Werner Burau zum 70. Geburtstag gewidmet     

UV/Vis Spectroscopic Properties of N -(2′-Hydroxy-4′- N , N -dimethyl-aminobenzylidene)-4-nitroaniline in Various Solvents and Solid Environments

 N-(2′-Hydroxy-4′-N,N-dimethylaminobenzylidene)-4-nitroaniline [HDBN] has been used as a model for investigating intra- and intermolecular D–A (donor–acceptor) interactions in various environments by means of UV/Vis spectroscopy. UV/Vis spectra of HDBN have been measured in various solvents, ethanolic solutions of different pH, adsorbed on silica, and in the solid state. A bathochromic shift of ν_max is observed with increasing the dipolarity/polarizability and HBD (hydrogen bond donor) capacity of the solvent, which is described by means of a multiple LSE (linear solvation energy) relationship in terms of the empirical Kamlet-Taft solvent polarity parameters. The adsorption of HDBN on Aerosil^? 300-silica particles in non-HBA (hydrogen bond acceptor) solvents is explained in the same sense. Mobile protons and sol–gel entrapping cause a hypsochromic shift due to protonation of the lone electron pair of the 4′-N,N-dimethylamino group. Hydroxide ions attack the 2′-hydroxy group which causes a bathochromic shift. A strong intramolecular hydrogen bond between the 2′-hydroxyl hydrogen and the imine nitrogen atom is present in the solid-state structure causing an unprecedented bathochromic shift.