Herrn Professor Dr. Dr. h. c. mult. J. F. K. Huber

Ohne Zusammenfassung     

Le Groupe de Recherche du C.R.N.S. Application des Reactions Nucleaires a l'Analyse Chimique G.A.R.N.A.C.

In this article the research topics dealt with at Research Group for Applications of Nuclear Reactions to Chemical Analysis (GARNAC) are described. Particular emphasis is laid on the main contribution of the GARNAC to the development and the evolution of charged particle activation analysis, evolving with the analytical studies performed and with the scientific and technical progress realized in material and semiconductors science.      

Gaspolarographie. II. Mitt.

Zusammenfassung Stickstoffdioxid, Stickstoffmonoxid, Distickstofftrioxid und Distickstoffmonoxid sind in wasserfreiem Dimethylsulfoxid polarographisch erfaßbar.

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Summary Nitrogen dioxide, nitrogen, monoxide, nitrogen trioxide, and nitrous oxide can be detected polarographically in anhydrous dimethylsulfoxide.

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Résumé On peut déceler le peroxyde d'azote, l'oxyde azotique, l'anhydride azoteux et l'oxyde azoteux par polarographie dans le diméthylsulfoxyde anhydre.

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Herrn Prof. Dr.A. A. Benedetti-Pichler zum 70. Geburtstag gewidmet.

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Für die Unterstiitzung der Untersuehungen wird der Regierung der USA gedankt.     

Ein Teleskop-Brenner. D.R.G.M.

Ohne Zusammenfassung     

60th Birthday of Prof. Dr. Dr. h.c. Heino Finkelmann

This section contains news of the macromolecular community all over the world. Articles about, for example, people, projects, and market trends are welcome. Suggestions should be sent to the editorial office of the Macromolecular journals, preferably by E‐mail to macromol@wiley‐vch.de. The editorial office decides which articles will be published.     

Oxazolochlorins. 14.

The structure of 8‐oxo‐5,10,15,20‐tetraphenyl‐7‐oxaporphyrin N²⁴‐oxide, C₄₃H₂₈N₄O₃, (4B), shows that N‐oxidation of the pyrrole opposite the oxazolidone group cants the pyrrole out of the mean plane of the chromophore. This also affects the oxazolidone group, which is also slightly canted out. This conformation is qualitatively similar to that of the parent meso‐tetraphenylporphyrin N‐oxide, but dissimilar to that of the porpholactone N‐oxide isomer 8‐oxo‐5,10,15,20‐tetraphenyl‐7‐oxaporphyrin N²²‐oxide, (4A), carrying the N‐oxide at the oxazolidone group. While the degree of canting of the N‐oxidized groups in both cases is comparable (and more pronounced than in the porphyrin N‐oxide case), in (4A) the pyrrolic groups adjacent to the N‐oxidized group are more affected than the opposing group. These differences in the conformational modes may contribute to rationalizing the distinctly different electronic properties of (4A) and (4B).     

Azole. 44.

The structure analyses of racemic 3‐chloro‐1‐(4‐morpholino‐5‐nitro­imidazol‐1‐yl)­propan‐2‐ol, C₁₀H₁₅ClN₄O₄, (II), and 3‐chloro‐1‐(5‐morpholino‐4‐nitro­imidazol‐1‐yl)­propan‐2‐ol, C₁₀H₁₅ClN₄O₄, (III), have been undertaken in order to determine the position of the morpholine residue in these two isomers. The morpholine residue in (II) is connected at the 4‐position, while in (III), it is connected at the 5‐position of the imidazole ring. The morpholine mean planes and nitro groups in the two compounds deviate from the imidazole planes to different extents. The nitro groups in (II) and (III) take part in the conjugation system of the imidazole rings. In consequence, the exocyclic C—N bonds are significantly shorter than the normal single Csp²—NO₂ bond and the nitro groups in (II) and (III) show an extraordinary stability on treatment with morpholine and piperidine [Gzella, Wrzeciono & Pöppel (1999). Acta Cryst. C 55 , 1562–1565]. In the crystal lattice, the mol­ecules of both compounds are linked by O—H?N and C—H?O intermolecular hydrogen bonds.     

Polysulfonylamines. CXXXII.

The crystal structure of the title compound, C₅H₇N₂⁺·C₁₂H₁₀NO₄S₂⁻, consists of two independent cation–anion pairs, A and B. Within each pair, the H—N—C—N*—H grouping (N*—H is the pyridinium function) and one N—S—O moiety of the anion are linked by N*—H⃛N and N—H⃛O hydrogen bonds to form an antidromic ring motif of type R²₂(8). The remaining amino donors give rise to N—H⃛O hydrogen bonds, connecting the ion pairs into A–B–A–B– chains. The structure testifies to the persistence of the R²₂(8) motif in question, which was previously detected as a highly robust supramolecular synthon in a series of onium di(methane­sulfonyl)­amidates. The structure is pseudosymmetric; the anion positions correspond to space group P2₁/n, but those of the cations do not.     

N. M. R. coupling constants

Approximate ab-initio calculations of NMR coupling constants are reported, for a number of small molecules. The agreement with experiment is erratic, and is shown to depend critically on the form of the excited state wavefunctions. This suggests that the use of an average energy approximation is far from valid.

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Zusammenfassung NMR Kopplungskonstanten werden für eine Anzahl von kleinen Molekülen mitgeteilt, wobei sich keine rechte Übereinstimmung mit dem Experiment ergibt. Es zeigt sich, daß die Werte kritisch von der Form der Wellenfunktion für die angeregten Zustände abhängen. Das läßt vermuten, daß die Verwendung eines mittleren Energienenners nicht zu empfehlen ist.

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Résumé Calculs ab-initio approchés des constantes de couplage NMR d'un certain nombre de petites molécules. L'accord avec l'expérience est erratique et dépend d'une façon critique de la forme des fonctions d'onde excitées. Ceci suggère que l'emploi d'une approximation d'«énergie moyenne» est loin d'être valable.

     

Hetero-Cope-Umlagerungen. 4. Mitteilung. Regiokontrollierte Indolsynthesen

Hetero-Cope-Rearrangements, Regio-Controlled Synthesis of Indoles The reaction of O-deprotonated N-phenylhydroxylamines 1 with various electron-deficient allenes 2 , 14 , 16 gives, via Michael addition and Cope-rearrangement, substituted anilines 5 , which are easily convertible into indoles 6 . In this manner, sulfoxides 17 , serve as equivalents of 2-vinylindoles. Diels-Alder reaction with this 2-vinylindole equivalent followed by indolisation affords isoquinuclidine derivative 21 which may be a useful precursor for the preparation of Iboga alkaloids.     

Prof. Dr. Dr. h. c. Fritz Feigl zum 70. Geburtstag

Ohne Zusammenfassung     

Professor Dr. phil., Dr. rer. nat. h. c., Dr. h. c., Dr. h. c. Wilhelm Klemm zum 70. Geburtstag

Ohne Zusammenfassung