Double diastereoselective [3,3]-sigmatropic aza-Claisen rearrangements

Asymmetric [3,3]-sigmatropic aza-Claisen rearrangement of the (Z)-N-allyl-N,O-silylketene aminal of (3S,4E,alphaR)-1-benzyloxy-3-(N-propionyl-N-alpha-methylbenzylamino)hex-4-ene furnishes (2S,3R,4E,alphaR)-N-alpha-methylbenzyl-2,3-dimethyl-7-benzyloxyhept-4-enamide in > 92% d.e.; rearrangement of the diastereomeric (3R,4E,alphaR)-(Z)-N,O-silylketene aminal proceeds with low diastereoselectivity.     

Radiation-induced solution polymerization of styrene in an engineering flow system

Radiation induced solution polymerization of styrene in methylene chloride in a small scale pilot plant utilizing a flow reactor is reported. Both conventional free radical and ionic polymerization have been achieved. With rigorous drying accomplished over molecular sieves the ionic mechanism predominates. Conclusive kinetic evidence as well as polymer properties substantiate radiation induced ionic polymerization for the first time in an engineering pilot plant. The validity of Williams' model is reinforced by this study and a survey of over 100 literature observations.     

A simple synthesis of 2(3H)-benzoxazolones using phenyl chloroformate

2(3H)-Benzoxazolones 3 can be prepared directly from the corresponding 2-aminophenols and phenyl chloroformate. The intermediate 2-hydroxy phenylcarbamates 2 are formed easily in aqueous alcohol solvent and these are converted rapidly to product, without their isolation, using one equivalent of sodium hydroxide. The synthesis accommodates a wide variety of substituents, including the easily hydrolyzed ethyl ester.     

Use of environmental scanning electron microscopy to image the spore adhesive of the marine alga Enteromorpha in its natural hydrated state

The environmental scanning electron microscope (ESEM) has been used to image the adhesive secreted by zoospores of the marine alga Enteromorpha as they settle on a surface, under natural, hydrated conditions. Results reveal a featureless, swollen gel-like adhesive pad, in contrast to the fibrillar character of the adhesive when imaged by standard SEM. At high spore densities the adhesive is confluent. Dynamic hydration/dehydration events were followed by changing the water vapour pressure in the sample chamber. Rapid hydration and swelling were observed indicating a very hygroscopic material. Adhesive footprints were detected when surfaces from which spores had been removed by water jetting were examined.     

Re-examination of the C NMR spectrum of xanthene: a revised correlation for the carbocyclic ring JCH meta-coupling constants in fused oxygen heterocycles

¹³C Chemical shifts and J_CH coupling constants are reported for xanthene and for some dimedone adducts containing a xanthene ring. A revised correlation pattern for the carbocyclic ring ³J_CH meta-couplings in fused oxygen heterocycles is proposed in which the magnitude of the interactions alternate around the ring.     

Synthetic approaches to 5,7- and 5,8-dimethoxyquinoline. Sonochemical dehalogenation of substituted 2,4-dichloroquinolines. Use of the 2D COLOC spectrum for the NMR assignment of 5,8-dimethoxyquinoline

Summary Sonochemical dehalogenation of 2,4-dichloroquinoline is very facile. However, with 5,7-dimethoxy-2,4-dichloroquinoline the reaction proceeds stepwise to provide the title dimethoxyquinolines which cannot be prepared via theSkraup reaction. The¹³C NMR chemical shift assignments for 5,8-dimethoxyquinoline are presented. These were made by utilising the coupling connectivities from the bridgehead carbons in the 2D COLOC spectrum.

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Synthese von 5,7- und 5,8-Dimethoxychinolin. Sonochemische Dehalogenierung von substituierten 2,4-Dichlorochinolinen. NMR-Spektroskopische Zuordnung von 5,8-Dimethoxychinolin mittels eines COLOC-Experiments

Zusammenfassung 2,4-Dichlorchinoline können sonochemisch leicht dehalogeniert werden. Mit 5,7-Dimethoxy-2,4-dichlorchinolin verläuft die Reaktion in mehreren Schritten zu den Titelverbindungen, die mittelsSkraup-Reaktion nicht hergestellt werden können. Das¹³C-NMR-Spektrum von 5,8-Dimethoxychinolin wurde, ausgehend von den Brückenkopfkohlenstoffatomen, mit Hilfe eines COLOC-Experiments zugeordnet.

     

Statistical properties of cosmic-ray scintillations at 250 GV

Summary We present the results of an amplitude domain analysis of cosmic-ray fluctuations in the interplanetary field at average rigidities of 250 GV. The experimental histograms are compared with the theoretical probability densities obtained by assuming linear behaviour and yield interesting results on extremal events. The approximate agreement is interpreted not as a proof that high-rigidity scintillations are indeed linear, but as possible evidence of noise contamination in this kind of analysis.

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Riassunto Sono presentati i risultati dell'analisi in ampiezza delle fluttuazioni di raggi cosmici di rigidità media 250 GV nel campo interplanetario. Gli istogrammi sperimentali sono compatibili con un comportamento lineare e permettono di ottenere interessanti indicazioni sugli eventi estremi. L'accordo è interpretato non come una prova che le scintillazioni ad alta rigidità sono in effetti lineari, ma piuttosto come possibile evidenza di contaminazione da background in questo tipo di analisi.

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Резюме Мы приводим результаты анализа амплитудной области флуктуаций космических лучей в межпланетном поле при средних жесткостях 250 GV. Экспериментальные гистограммы согласуются с теоретическими предсказаниями, полученными в предположении линейного поведения и дают интересные результаты для экстремальных событий. Полученное согласие интерпретируется не как доказательство того, что сцинтилляции при высокой жесткости действительно являются линейными, а как возможное подтверждение наличия шумового загрязнения в этом типе анализа.