Über N1- und N2-substituierte 2-Amino-5,6-dihydro-4(1H)-pyrimidinone

The reactions of the monosubstituted guanidines2 b-h with methyl acrylate in dimethylformamide or ethanol as solvent preferentially afford 1-substituted 2-amino-5,6-dihydro-4(1H)-pyrimidinones6 b-h. The structures of 1-hexyl- and 1-benzyl-4-pyrimidinones6 c, e and of the picrate of 1-phenylpyrimidinone6 g were proved by comparison with authentic samples, which were prepared from N-substituted ethyl 3-amino-propionates14 c, e andg and cyanamide. Accordingly,6 g is not identical with authentic 2-phenylaminopyrimidinone7 g (prepared from 2-methylthio-4-pyrimidinone10 and 2-thioxo-4-pyrimidinone12 respectively, compare¹⁰).N,N-Disubstituted guanidines2 i-m react with methyl acrylate in dimethylformamide as solvent to afford N²,N²-disubstituted 2-amino-5,6-dihydro-4-(1H)-pyrimidinones7 i-m. Action of morpholine-4-carboxamidine (21) on methyl acrylate in ethanol yields 2-morpholinopyrimidinone71 as byproduct and 3-ethoxy-N-[morpholino(amino)methylene]propionamide (91) as mainproduct.

Herrn Prof. Dr.Robert Ott mit den besten Wünschen zum 60. Geburtstag gewidmet.     

Bestimmung der Salpetrigsäure-Alkohol-Alkylnitrit-Gleichgewichte mit Hilfe der „Thermodynamik der Zwischenreaktionen” und Kinetik der O-Nitrosierung der Alkohole durch Nitritacidiumion

Zusammenfassung Die Gleichgewichtskonstanten der Reaktion der salpetrigen Säure mit Methanol, Äthanol, Propanolen und Butanolen in wäßriger Lösung bei 25° C wurden nach der kinetischen Methode der Gleichgewichtsbestimmung vonHermann Schmid mit Hilfe von Geschwindigkeitsmessungen der Phenolnitrosierung durch salpetrige Säure in alkoholhältiger wäßriger Lösung ermittelt. Die Geschwindigkeitskoeffizienten der O-Nitrosierung der Alkohole durch Nitritacidiumion wurden aus den ermittelten Gleichgewichtskonstanten und den bekannten Geschwindigkeitskoeffizienten der Wasserstoffionkatalysen der Alkylnitrithydrolysen berechnet und der Reaktionsmechanismus der Alkoholnitrosierung diskutiert.

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The equilibrium constants of the reaction of nitrous acid with methanol, ethanol, propanols and butanols in aqueous solution at 25° C were found-according to the kinetic method of the equilibrium determination byHermann Schmid ¹-by measurements of the phenol nitrosation by nitrous acid in alcoholic aqueous solution. The rate coefficients of the O-nitrosation of the alcohols by nitrosoacidiumion were calculated from the determined equilibrium constants and the known rate coefficients of the hydrogen ion catalyses of the alkyl nitrite hydrolyses and the mechanism of the alcohol nitrosation is discussed.

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Herrn o. Univ.-Prof. Dr. Dr. h. c.Friedrich Wessely zum 70. Geburtstage herzlichst gewidmet.     

The difference between the reactivities of azomethine bonds in metamitron in electrochemical and chemical reductions

Electrochemical reduction of a herbicide metamitron (4-amino-3-mefhyl-6-phenyl-1,2,4-triazin-5(4H)-one) in buffered aqueous solutions occurs on the protonated 1,6-carbon-nitrogen double bond. The 2,3-double bond in the resulting 1,6-dihydrometamitron is electrochemically reduced at considerably more negative potentials. In reaction with borohydride the 2,3-double bond is reduced first. Reduction of the 1,6-double bond is very little influenced by replacing the 2,3-double bond by the -NHCH- grouping in 2,3-dihydrometamitron.     

Effect of surface‐grafted ionic groups on the performance of cellulose‐fiber‐reinforced thermoplastic composites

The influence of the surface chemistry of the cellulose fiber and polymer matrix on the mechanical and thermal dynamic mechanical properties of cellulose‐fiber‐reinforced polymer composites was investigated. The cellulose fiber was treated either with a coupling agent or with a coupling‐agent treatment followed by the introduction of quaternary ammonium groups onto the fiber surface, whereas the polymer matrix, with opposite polar groups such as polystyrene incorporated with sulfonated polystyrene and poly(ethylene‐co‐methacrylic acid), was compounded with the fiber. The grafting of the fiber surface was investigated with Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy. Experimental results showed that an obvious improvement in the mechanical strength could be achieved for composites with an ionic interface between the fiber and the polymer matrix because of the adhesion enhancement of the fiber and the matrix. The improved adhesion could be ascribed to the grafted ionic groups at the cellulose‐fiber surface. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2022–2032, 2003     

Thermodynamics of miscible polymer blends using a concentration-dependent χ parameter

The Flory equation-of-state theory, as expressed by Patterson and co-workers, has been applied to two miscible polymer blends: poly(vinyl chloride)/poly(ε-caprolactone) and poly(methyl methacrylate)/poly(vinylidene chloride). For both blends, the variation of the polymer-polymer interaction parameter, χ, as a function of composition, is mostly small and can be accounted for by the Flory theory. However, for poly(vinyl chloride)/poly(ε-caprolactone) blends, at high poly(ε-caprolactone content), the large variation of χ as a function of concentration can be explained by a variation of the surface-to-volume ratio of the polymers in the mixture with blend composition. The variations of the surface-to-volume ratios determined in this study agree with those reported in the literature using small-angle x-ray scattering.     

Microencapsulation of nisin in alginate-cellulose nanocrystal (CNC) microbeads for prolonged efficacy against Listeria monocytogenes

The present study was undertaken to develop edible nisin-microencapsulated beads in order to inhibit growth of Listeria monocytogenes in ready-to-eat (RTE) ham. Different concentrations of nisin (16, 31, and 63 μg/ml) were microencapsulated into alginate-cellulose nanocrystal beads. Microencapsulation kept the available nisin (63 μg/ml) content 20 times greater compared with free nisin (63 μg/ml) during 28 days of storage at 4 °C. Results showed that 63 μg/ml microencapsulated nisin exhibited 31.26 μg/ml available nisin content after 28 days of storage at 4 °C, whereas there was no available nisin content left for free nisin. Cooked ham slices were then coated by the microencapsulated nisin beads, inoculated with L. monocytogenes [~3 log colony-forming units (CFU)/g], and stored at 4 °C under vacuum packaging for 28 days. The beads containing 16, 31, and 63 μg/ml nisin significantly (P ≤ 0.05) reduced the L. monocytogenes counts by 2.65, 1.50, and 3.04 log CFU/g after 28 days of storage compared with free nisin. Furthermore, microencapsulated nisin beads did not change the physicochemical properties (pH and color) of RTE ham during storage.     

A new cyclization to fused pyrazoles tunable for pericyclic or pseudopericyclic route: an experimental and theoretical study

2-Pyrazinyl (2) and 3-pyridazinylketone arylhydrazones (6) and their benzologues undergo a ring closure reaction to yield pyrazolo[3,4- b]pyrazines (4) and pyrazolo[4,3- c]pyridazines (7), respectively, in acceptable to good yields. The reaction was found to be accelerated by using acidic or basic conditions. Quantum chemical calculations suggest the key step of the mechanism to be a direct cyclization; analysis of aromaticity based on computed magnetic properties revealed its medium-dependent pericyclic or pseudopericyclic character. The cyclization reaction has also been extended for the synthesis of related ring systems ( 9, 12, 14).     

Finite-temperature collective dynamics of a Fermi gas in the BEC-BCS crossover

We report on experimental studies on the collective behavior of a strongly interacting Fermi gas with tunable interactions and variable temperature. A scissors mode excitation in an elliptical trap is used to characterize the dynamics of the quantum gas in terms of hydrodynamic or near-collisionless behavior. We obtain a crossover phase diagram for collisional properties, showing a large region where a nonsuperfluid strongly interacting gas shows hydrodynamic behavior. In a narrow interaction regime on the BCS side of the crossover, we find a novel temperature-dependent damping peak, suggesting a relation to the superfluid phase transition.     

A new synthetic approach to phenothiazine-2-amines

Elaboration of a Buchwald-Hartwig protocol for the introduction of amino functions to position 2 of the phenothiazine ring system has opened a new access to various N-alkyl and N-dienyl phenothiazines bearing secondary amines, tertiary amines, and amide moieties. Hydrolysis of the amido derivatives gave unsubstituted phenothiazine-2-amines. This protocol provides an easy access to phenothiazine-2-amines starting from the commercially available starting compounds.