Die Konstitution der Michael-1,3-Addukte von Cyanessigsäureäthylester an konjugierte Systeme

Zusammenfassung Es wird gezeigt, daß bei der Einwirkung von Cyanessigester auf p-Benzochinon bzw. auf 2,4-Dimethyl-o-chinolacetat Verbindungen entstehen, denen auf Grund der IR-Spektren die Konstitution von Amino-benzofurancarbonsäure-estern zugeschrieben werden muß. Sowohl bei alkalischer als auch bei saurer Verseifung erfolgt Sprengung des Furanringes, intermediär entsteht ein Nitril, das sehr leicht weiter zur Säure bzw. einem Lacton verseift wird. Die Aminogruppe der genannten Aminobenzofuranderivate ist unter energischen Bedingungen zu einer Diacetylaminogruppe acetylierbar. Die Monoacetylverbindung tritt nur als schwer isolierbares Zwischenprodukt auf und ist besser unter milden Verseifungsbedingungen aus der Diacetylverbindung zugänglich. Die Aminogruppe ist unter üblichen Bedingungen nicht titrierbar; sie verhält sich in diesem Belang chemisch völlig anders als die des Anthranilsäureäthylesters, der titrierbar ist. Im IR-Spektrum zeigen hingegen Anthranilsäureäthylester und Aminobenzofuransäureäthylester sehr große Ähnlichkeiten. Eine Erklärung dieser Diskrepanzen hinsichtlich des chemischen Verhaltens und der spektralen Eigenschaften kann derzeit nicht gegeben werden.Mit 1 Abbildung     

Die Charaktere der symmetrischen Gruppe

Ohne ZusammenfassungHerrnOskar Perron zum 80. Geburtstag am7. Mai 1960     

φ production in In–In collisions at 158 A GeV

The NA60 experiment has measured muon pair production in In–In collisions at 158 AGeV at the CERN SPS. This paper presents a high statistics measurement of φ→μ μ meson production. Differential spectra, yields, mass and width are measured as a function of centrality and compared to previous measurements in other colliding systems at the same energy. The width of the rapidity distribution is found to be constant as a function of centrality, compatible with previous results. The decay muon polar angle distribution is measured in several reference frames. No evidence of polarization is found as a function of transverse momentum and centrality. The analysis of the p _T spectra shows that the φ has a small radial flow, implying a weak coupling to the medium. The T _eff parameter measured in In–In collisions suggests that the high value observed in Pb–Pb in the kaon channel is difficult to reconcile with radial flow alone. The absolute yield is compared to results in Pb–Pb collisions: though significantly smaller than measured by NA50 in the muon channel, it is found to exceed the NA49 and CERES data in the kaon channel at any centrality. The mass and width are found to be compatible with the PDG values at any centrality and at any p _T : no evidence for in-medium modifications is observed.     

para‐Sulfonated Calixarenes Used as Synthetic Receptors for Complexing Photolabile Cholinergic Ligand

The water‐soluble tetra‐, hexa‐ and octasulfonated calix[4]arenes, calix[6]arenes, and calix[8]arenes 1 – 3 , respectively, were investigated as potential synthetic receptors for photolabile cholinergic ligand A , a photolytic precursor of choline. Ligand A is a bifunctional molecule carrying a photolabile 2‐nitrobenzyl group at one end and a choline moiety at the other end. Results from NMR studies have shown that calixarenes 1 – 3 form stable 1 : 1 complexes with A , having similar binding potential to that observed with the cholinergic enzymes acetylcholinesterase and butyrylcholinesterase. Further studies have suggested that calix[8]arene forms a ditopic complex by binding concomitantly to both the cationic choline moiety and the aromatic photolabile group of A , whereas calix[4]arene and calix[6]arene form monotopic complexes with A . The ditopic complex between calix[8]arene and A results from mutually induced fitting process, while the monotopic complexes between calix[4]arene and A can be regulated by pH: at neutral pH, calix[4]arene specifically binds the cationic choline moiety, while, at acidic pH, it complexes unselectively both the cationic choline moiety and the aromatic group of A . Our results show that para‐sulfonated calixarenes are versatile artificial receptors which bind in various ways to the bifunctional photolabile cholinergic ligand A , depending on their size, geometry, and state of protonation.     

Direct determination of polycyclic aromatic hydrocarbons in solid matrices using laser desorption/laser photoionization ion trap mass spectrometry

The development and characterization of a new instrument for solid sampling which couples IR laser desorption followed by UV laser photo-ionization and analysis using an ion trap mass spectrometer has been investigated. For calibration, a new type of solid sample preparation involving activated charcoal as the solid substrate was used. This solid sample provided a steady signal for several thousand laser shots, which allowed optimization of the experimental procedure. It was found that both the IR and UV intensity and the delay between them play an important role in both the magnitude and type of signals observed. A method of gas phase accumulation with multiple laser shots was examined. Finally, this technique was demonstrated to be effective in providing direct qualitative information for N.I.S.T. SRM 1944 river sediment sample with no sample pre-treatment.     

Gas-chromatographic determination of pesticide residues after clean-up by gel-permeation chromatography and mini-silica gel-column chromatography

A new extraction and partition step was introduced into the well established multi-residue method of Specht and Tillkes (DFG method S 19) replacing dichloromethane by ethyl acetate/cyclohexane (1+1). In addition, more simple working conditions were obtained. Results of fortification experiments with organochlorine, organophosphorus and organonitrogen pesticides showed good agreement with those obtained by the formerly published method.