Induced circular dichroism and structural assignment of the cyclodextrin inclusion complexes of bicyclic azoalkanes

The stoichiometries and binding constants of the host-guest complexes between the bicyclic azoalkanes 1-6 and alpha-, beta-, and gamma-cyclodextrins (CDs) and the induced circular dichroism (ICD) of the complexes were analyzed. Assisted by proximity relationships obtained from 2D ROESY NMR spectra, the signs and intensities of the ICD spectra are interpreted in terms of the solution structures (co-conformations) of the CD complexes. The ICD assignments are based on the orientation-intensity ICD rules of Harata and Kodaka, which relate the ICD signs and intensities to the relative orientation of the electric dipole transition moment of the n,pi azo chromophore to the CD axis. The influence of the size of the guest and the host is discussed and the effect of introducing an additional chromophore (either a phenyl or a second azo group) on the ICD spectra is demonstrated.     

Novel UDP-glycal derivatives as transition state analogue inhibitors of UDP-GlcNAc 2-epimerase

The "epimerisation" of UDP-GlcNAc to ManNAc, the first step in the biosynthesis of sialic acids, is catalyzed by UDP-GlcNAc 2-epimerase. In this paper we report the synthesis of transition state based inhibitors of this enzyme. To mimic the assumed first transition state of this reaction (TS 1), we designed and synthesized the novel UDP-exo-glycal derivatives 1-4. We also report herein the synthesis of 5 and 6, the first C-glycosidic derivatives of 2-acetamidoglucal, and the synthesis of the ketosides 7 and 8, which were designed as bis-substrate analogue and bis- product analogue, respectively, to mimic the second step of the reaction via the assumed second transition state TS 2.     

Phototropie von niedergeschlagenem AgBr-Aerosol

Zusammenfassung Mit einer Drahtexplosion von Silberdraht in einer Brom/Argon-Atmosphäre wurde AgBr-Aerosol hergestellt und auf einer Quarzglasplatte niedergeschlagen. Bei Bestrahlung der so gebildeten Schicht im UV-Spektralbereich von 300–400 nm ergab sich eine Schwärzung, die nach Unterbrechung der Einstrahlung wieder zurückging (Phototropie), wenn die Schicht mit Bromdampf in Berührung stand. Mit Laserlichtbeleuchtung wurde an mehreren Schichten der zeitliche Verlauf der Remission gemessen und dabei Bestrahlungsstärke, Bromdampfdichte und Belegungsdichte der Schicht variiert. Zunehmender Bromgehalt hat aufhellende Wirkung. Die gemessenen Schwärzungs- und Regenerationszeiten sind etwa 10mal kleiner als die von handelsüblichen phototropen Gläsern. Zur phänomenologischen Deutung der Ergebnisse wurde ein einfaches reaktionskinetisches Modell aufgestellt, das 4 Konstanten enthält, die aus dem Experiment bestimmt wurden. Dabei wurde die Konzentrationsabhängigkeit der die Remission kennzeichnendenKubelka-Munk-Funktion herangezogen.Summary A silver wire exploding in an atmosphere of bromine and argon provides the generation of a silver bromide aerosol which is precipitated on a quartz glass plate. As the layer formed in this way is submitted to ultraviolet radiation ranging from 300 to 400 nm, a blackening occurs which, after interruption of the emitted radiation, decreases again (phototropy) when the layer is in contact with the bromine vapor. A laser beam is used to measure the development with time of the reflectance of various layers. For this the irradiante, bromine vapor concentration, and surface density of the layer are being varied. The increase in the content of bromine causes the blackening to attenuate. Both the measured blackening and regeneration durations are approximately ten times shorter than those of commercially available phototropec glasses. In order to explain these phenomena as well as the relating results, a simple kinetic model was established including four constants which were determined from the experiment. For this theKubelka-Munk function was used characterizing the reflectance as a function of concentration.

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Mit 10 Abbildungen     

Darstellung und Eigenschaften von π-Cyclopentadienylrhodium-bis(tert.-phosphit)-Komplexen

The half-sandwich type compounds C₅H₅Rh[P(OR)₃]₂ (R = CH₃, C₂H₅, C₆H₅, p-CH₃C₆H₄, p-ClC₆H₄) have been prepared from [(P(OR)₃)₂RhCl]₂ and NaC₅H₅. The NMR. data as well as the IR. and mass spectra of the new compounds will be discussed. The preparation of C₅H₅Rh(CO)P(OC₂H₅)₃ is also reported.     

Synthesen von Heterocyclen, 146. Mitt.: Zur Synthese polymerer Indigofarbstoffe mit potentiellen Halbleitereigenschaften

Zusammenfassung Die Darstellung von polymeren Indigofarbstoffen (PI) nach dem Verfahren vonZiegler undKappe ^{2, 3} wird beschrieben. Ausgehend von Benzidin (1 a) und Tolidin (1 b) erhält man so diePI 6 a bzw.6 b. In analoger Weise wird aus Tetrahydrochinoxalin (7), der N,N-überbrücktePI 12 gewonnen.

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Syntheses of heterocycles, CXLVI: The synthesis of polymeric indigos with potential semiconductor properties

The synthesis of polymeric indigos (PI) according to the procedure ofZiegler andKappe ^{2, 3} is described. Starting with benzidine (1 a) or tolidine (1 b) thePI 6 a and6 b, resp., are obtained. In a similar way the N,N-bridgedPI 12 is synthesized from tetrahydroquinoxaline (7).

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Aus den Dissertationen vonH. G. Foraita undL. F. Werner, Universität Graz, Januar bzw. Juni 1963.     

Über die Eigenschaften eines neuen Chromogens für die Blutzuckerbestimmung nach der GOD/POD-Methode

A method is described which uses the ammonium salt of 2,2′-azino-di-[3-ethyl-benzothiazoline-(6)-sulphonic acid] as a redox indicator for the photometric determination of glucose with glucose oxidase and peroxidase. The sensitivity of this method is more than four times better than the method using o-dianisidine. The test solution including all reagents necessary for the determination of glucose is highly stable.     

Finitely correlated states on quantum spin chains

We study a construction that yields a class of translation invariant states on quantum spin chains, characterized by the property that the correlations across any bond can be modeled on a finite-dimensional vector space. These states can be considered as generalized valence bond states, and they are dense in the set of all translation invariant states. We develop a complete theory of the ergodic decomposition of such states, including the decomposition into periodic Néel ordered states. The ergodic components have exponential decay of correlations. All states considered can be obtained as local functions of states of a special kind, so-called purely generated states, which are shown to be ground states for suitably chosen finite range VBS interactions. We show that all these generalized VBS models have a spectral gap. Our theory does not require symmetry of the state with respect to a local gauge group. In particular we illustrate our results with a one-parameter family of examples which are not isotropic except for one special case. This isotropic model coincides with the one-dimensional antiferromagnet, recently studied by Affleck, Kennedy, Lieb, and Tasaki.     

Gitterpunkte in Lemniskatenscheiben

Let G (R) denote the number of lattice points (,) **Z² in the domain B(R) bounded by the lemniscate (x²+y²)²=2R² (x²–y²) and put P(R)=G(R)-R²(R² being the area of B(R)). The purpose of this paper is to determine the order of magnitude of P(R) for large R by proving the asymptotic relation (3). An analogous result is given for the eight curve x⁴=R² (x²–y²).     

Abbau von Palustrin zu (−)-Dihydropalustraminsäure ((2R, 6S, 1′S)-[6-(1′-Hydroxypropyl)-2-piperidyl]essigsäure) und Struktur von Palustrin und Palustridin. Mitteilung über Schachtelhalmalkaloide

Degradation of palustrin to (?)-dihydropalustramic acid ((2R,6S,1′S)-[6-(1′-hydroxypropyl)-2-piperidyl]acetic acid), and the structure of palustrin and palustridin The structure of the macrocyclic alkaloid palustrin is shown to be 1a . Its piperidine unit can be obtained as (?)-dihydropalustramic acid ( 6a ) by the following sequence of degradation reactions (Scheme 1): catalytic hydrogenation of 1a followed by methylation and Hofmann degradation provides the allyl base 4 . the regioselectivity of the Hofmann elimination is explained by intramolecular proton abstraction at C(3) by C(18)-O^?. Catalytic reduction of 4 and subsequent acidic hydrolysis yielded 6a and N, N-dimethylputrescine (?N,N-dimethyl-1,4-butanediamine; 7 ). Loss of the N-alkyl group in the formation of 6a occurs during the catalytic hydrogenation step. This interpretation is supported by the results of model experiments. The position of the double bond in 1a is deduced from the IR. spectrum of the bromo-δ-lactone 19 prepared by treatment of 1a with N-bromosuccinimide at pH 4 (Scheme 3). Some of our previously published results on the degradation of dihydropalustrin ( 2a ) are obviously at variance with the newly proposed structure for palustrin ( 1a ). They can easily be explained by assuming a partial hydrogenolysis of the C(17)-N(1) bond during the preparation of dihydropalustrin from palustrin. Periodate cleavage of dihydropalustramic acid methyl ester ( 6b ) liberates propionaldehyde, which can be trapped by working at pH 7.5 (Scheme 2); at lower pH values it condenses rapidly with the simultaneously generated 3,4,5,6-tetrahydropyridine derivative 15 . The structure of the condensation product is proposed to be 16 on the basis of the isolation of its hydrogenation product, an isomeric dihydropalustramic acid ( 17 ).