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Ohne Zusammenfassung

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Book reviews

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Notices bibliographiques

     

On the Claisen Rearrangement of Allyl Ethyl Ketene Acetals Generated in situ via Benzeneselenenic Acid Eliminiation

Mixed acetals 7 of benzeneseleninylacetaldehyde, prepared by a simple 2-step procedure from mono- and bicyclic allylic alcohols 5 , undergo benzeneselenenic acid elimination to transient ketene acetals 8 which afford γ, δ-unsaturated esters 9 via the ester Claisen rearrangement (Scheme 2). Under the same conditions selenoxide 7h derived from benzyl alcohol 5h is converted back to benzyl alcohol with the concomitant formation of ethylphenylselenoacetate 12 .     

The Crystal structure of 2-Diisopropylamino-3,7-dehydrotropone

Die erste Röntgenstrukturanalyse eines 3,7-Dehydrotropon ( 1 )-Derivates, nämlich von 2-Diisopropylammo-3,7-dehydrotropon ( 4 ) zeigt das Ringsystem in 4 als planaren Bicyclus mit nahezu C_2V-Symmetrie. Dementsprechend enthalten Dehydrotropone formell zwei trans-konfigurierte Doppelbindungen in einem 7-gliedrigen Ring; auch das O-Atom und das N-Atom mit seinen Ligandatomen liegen in derselben Ebene wie die Ringatome. Die Bindung zwischen den beiden C-Atomen, welche die Heteroatome tragen, (C(1) and C(2)), ist wesentlich langer (1,56 Å) als die anderen Bindungen im Ringsystem (1,37-1,46 Å). Dies impliziert eine ‘push-pull’-π-Elektronen-Delokalisierung, in der auch das O-und das N-Atom involviert sind, und macht eine ‘aromatische’ Ring-Delokalisierung weniger wahr-scheinlich. Im Gegensatz zu 2-(t-Butyl)-3,7-dehydrotropon ( 3 ) existiert das 2-Diiso-propylamino-3,7-dehydrotropon ( 4 ) im Kristall als Monomeres, was dem stabili-sierenden Einfluss der ‘push-pull’-Delokausierung zugeschrieben werden kann.     

Potential non-steroidal estrogens and antiestrogens,IV Organic azides in heterocyclic synthesis,part 13: Synthesis of aza- and diazacoumestrols via azido derivatives

Summary 4-Chloro-3-aryl-coumarins and quinolones2 a–e undergo thermolytic ring closure by reaction with sodium azide in refluxing dimethyl formamide to yield indolo[3,2-c]coumarins and indolo[3,2-c]quinolin-6(5H)-ones6 a–e. In the case of the coumarin2 a the azido coumarin5 can be isolated. The mono- and diazacoumestrol-dimethylethers6 a–c are converted into the coumestrol analogues7 a–c and their diacetyl derivatives8 a–c.

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Potentielle nichtsteroidale Östrogene und Antiöstrogene, 4. Mitt.: Organische Azide in der Heterocyclensynthese, Teil 13: Synthese von Aza- und Diazacumöstrolen über Azidzwischenstufen

Zusammenfassung 4-Chlor-3-arylcumarine und-chinolone2 a–e reagieren thermolytisch mit Natriumazid in siedendem Dimethylfomamid unter Ringschluß zu Indolo[3,2-c]cumarinen und Indolo[3,2-c]chinolin-6(5H)-onen6 a–e. Nur aus dem Cumarinderivat2 a kann das zwischenzeitlich gebildete Azidocumarin5 isoliert werden. Die so erhaltenen Mono- und Diazacumöstroldimethylether6 a–c werden in die entsprechenden Cumöstrole7 a–c und ihre Diacetylderivate8 a–c umgewandelt.

     

Huang diffuse scattering from interstitials in a general orthorhombic and tetragonal lattice

Using the continuum theory of linear elasticity, Huang diffuse scattering (HDS) has been calculated from self-interstitials in a general orthorhombic and tetragonal lattice. Various defect configurations are represented according to the point group symmetry of the defect site. The contribution toHDS from all possible equivalent orientations (assumed to be equally populated) of the defect configuration is averaged. The limitations ofHDS in discriminating between defect configurations having the same long-range symmetry are discussed, considering some special cases.     

5-(N-Arylnortropan-3-yl)- and 5-(N-Arylpiperidin-4-yl)-2,4-diaminopyrimidines. Novel Inhibitors of Dihydrofolate Reductase

Based on a computer-assisted analysis of the three-dimensional structure of the binary complex of E.coli dihydrofolate reductase (DHFR) with methotrexate, 5-(N-arylnortropan-3-yl)- and 5-(N-arylpiperidin-4-yl)-2,4-diaminopyrimidines 2 and 4 were designed as inhibitors of DHFR. Syntheses of the designed compounds have been carried out. The most potent compound 2a inhibited E. coli DHFR with K_i = 0.49.10^?9M. The activities within the series of compounds synthesized could be rationalized by molecular-modelling experiments which served as the basis of this work. Several compounds within the presented series exhibit antimalarial activities in vitro and in vivo.     

The oxidative decarboxylation of polyaminocarboxylic acids

Summary The rates of oxidation of four chelating agents, NTA, EDTA, CDTA, and DTPA with Ce(IV), in sulfuric acid media, were determined spectrophotometrically by a stopped-flow technique. The reductive ability is in the order CDTA > EDTA > DTPA > NTA. The influence of varying the acidity of the medium was studied, and in each case a maximum in the rate constant vs. [H⁺] plot was observed. A possible interpretation of the reactivities and the influence of acidity is advanced.

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Oxydative Decarboxylierung von PolyaminocarbonsäurenII. Vergleichende kinetische Untersuchung der Oxydation von NTA, ÄDTA, CDTA und DTPA mit Ce(IV) in saurer Lösung

Zusammenfassung Die Oxydationsgeschwindigkeiten von 4 Chelaten (NTA, ÄDTA, CDTA und DTPA) mit Ce(IV) in saurer Lösung wurden spektrophotometrisch mit Hilfe der stopped-flow-Technik bestimmt. Die Reduzierfähigkeit nimmt in der Reihenfolge CDTA > ÄDTA > DTPA > NTA ab. Der Einfluß verschiedener Säuregehalte in der Lösung wurde untersucht, und in jedem Fall wurde ein Maximum in der graphischen Darstellung der Geschwindigkeitskonstante gegen [H⁺] beobachtet. Eine mögliche Erklärung des Reaktionsvermögens und des Säureeinflusses wird gegeben.

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Part I: Z. Anal. Chem. 246, 231 (1969).     

The Chemistry of Coumarin Derivatives. Part 5. Unusual course of the reaction of 4-hydroxycoumarin and aliphatic aldehydes

The reaction of 4-hydroxycoumarin and certain aliphatic aldehydes affords 1:1 or complex 2:2 adducts besides (or in place) of the expected 2:1 bis(coumarin) adducts. Reaction with heptanal, cyclohexanecarbaldehyde, and pivalaldehyde are reported as representative. The structure of the reaction products was established by spectroscopical techniques, including X-ray analysis, and their formation was mechanistically rationalized. Some of the 1:1 adducts are synthetically useful for the preparation of 3-alkyl-4-hydroxycoumarins.     

Metabolic Profile of Agropyron repens (L.) P. Beauv. Rhizome Herbal Tea by HPLC-PDA-ESI-MS/MS Analysis

Agropyron repens (L.) P. Beauv. (couch grass) is a world-wide infesting rhizomatous plant with pharmacological applications. Chemical research is focused on its allelopathic and anti-inflammatory components, which are mainly present in the essential oil. Conversely, the aqueous extracts have been sparingly investigated, although the herbal tea is by far the most used formulation. To fill the gap, the metabolic profile of Agropyron repens rhizome herbal tea was investigated by electrospray ionization (ESI) tandem–mass spectrometry (MS/MS); the phenolic profile was investigated by HPLC-PDA-ESI-MS/MS. ESI-MS fingerprinting was provided, evidencing diagnostic ions for saccharides, organic acids and amino acids. The HPLC-PDA-ESI-MS/MS analysis evidenced at least 20 characteristic phenolic compounds, the most representative being caffeoyl and feruloyl quinic esters, followed by coumaric, caffeic and ferulic acids, and hesperidin among flavonoids. In addition, the essential amino acid tryptophan was identified for the first time. The results suggest new perspectives of applications for Agropyron repens rhizome.