Intramolecular meerwein reactions of the anthraquinone system. Synthesis,X-ray structural analysis and spectroscopic properties of anthra[9,1-bc:10,5-b'c']tetrahydrodipyran derivatives

Meerwein reactions of 1,5-anthraquinone bis(diazonium hydrogen sulfate) with sufficiently activated olefins, such as acrylonitrile, acrylic esters, methacrylonitrile and its esters, styrene and α-methylstyrene yielded derivatives of the new heterocyclic system anthra[9,1-bc:10,5-b'c']-2,3,7,8-tetrahydrodipyran. Isolation of derivatives was realized and yields enhanced by using dimethyl methylphosphonate as reaction medium. Compounds 5–18 were isolated as mixtures of diastereomers, some of which were separated by crystallization. Proof of structure and stereochemistry was obtained for some of the compounds by X-ray crystallographic analysis. The ¹H- and ¹³C-nmr data provided further support. Surprisingly large chemical shift differences between some of the proton signals of isomers were observed although the two asymmetric centers are far apart through bonds and through space. The mechanism of formation is explained on the basis of redox modulation of a charge transfer complex in which the aliphatic radical attacks the oxygen atom of the anthraquinone. It is proposed to classify this new type of reaction as an intramolecular Meerwein reaction.     

Modellrechnungen zum Dendriten-Wachstum in partiell-kristallinen Hochpolymeren

Zusammenfassung Überstrukturen in partiell-kristallinen Thermoplasten liegen oft in Gestalt von Sphärolithen vor. Es wird versucht, ihre Entstehung auf behindertes Dendritenwachstum zurückzuführen. Die durch das Simulationsmodell beschriebenen Strukturen werden mit experimentell beobachteten verglichen.

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Superstructures in partial-crystalline thermoplastics often show the shape of spherulites. The reason of this can be a handicapped growth of dendrites. The structures obtained by a simulation model are compared with those obtained by experiments.

     

Cumulated double bond systems as ligands : X. N-sulfinylaniline complexes of rhodium(I) and iridium(I) of the type [MCl(PR3)2L] in which L is coordinated via the π-NS and via the sulfur atom respectively; crystal and molecular structure of [RhCl(P-i-Pr3)2(4-MeC6H4NSO)]; determination of the 1J(103Rh15N) by 15N NMR spectroscopy

Each of the compounds [MCl(Pr₃)₂(ArylNSO)] (M = Rh^I, Ir^I; R = i-Pr, Cy: Aryl = C₆H₅, 4-MeC₆H₄, 4-ClC₆H₄, 2,4,6-Me₃C₆H₂ appears to exist as two isomers both in the solid state and in solution. The molecular and single crystal structure of one of the isomers of [RhCl(P-i-Pr)₃)₂(4-Me₆H₄NSO)] shows that the N-sulfinylaniline ligand is in the cis-configuration and coordinated to the rhodium atom via the sulfur-atom. The ligand lies in a plane which includes the rhodium atom and is in agreement with the Rh-S distance of 2.10 Å. IR results of the compounds (solid and solutions), ²¹P NMR data and ¹⁵N NMR of a ¹⁵N labelled compound, which yielded a ¹⁰³Rh¹⁵N coupling constant of 15.5 Hz, show that in the second isomer the N-sulfinylaniline ligand is probably bonded to the metal atom via the π-NS bond.The ratio of the metal-π-NS bonded isomer and the metal-S bonded isomer decreases in the order Aryl = 4-ClC₆H₄ > C₆H₅ > 4-MeC₆H₄; R = i-Pr > Cy and M = Rh > Ir. The interconversion of the two isomers is intramolecular and becomes observable on the ³¹P NMR time scale at about 40° C for M = Rh.In the case of [Ir(P-i-Pr₃)₂(4-MeC₆H₄NSO)], cyclometallation of the sul- finylaniline is observed via the ortho-carbon atom, whereas cyclometallation via P-i-Pr₃ is observed when the ortho-positions are blocked by methyl groups, e.g. when L = 2,4,6-Me₃C₆H₂NSO.     

Aktivierungsanalytische Sauerstoffbestimmung mit schnellen Reaktorneutronen

Summary Oxygen can be determined by the nuclear reaction ¹⁶O (n, p) ¹⁶N initiated by fast reactor neutrons. The automatic irradiation and counting system which is used in the Munich research reactor for non-destructive oxygen determination is described. The activation by thermal neutrons is suppressed by the installation of a cadmium shield around the pneumatic tube at the irradiation position. Oxygen has been determined in the presence of many elements to find out which elements disturb the oxygen activation analysis.Zusammenfassung Sauerstoff läßt sich aktivierungsanalytisch mit schnellen Reaktorneutronen über die Kernreaktion ¹⁶O (n, p) ¹⁶N bestimmen. Die automatische Bestrahlungs- und Meßanlage, die die Durchführung solcher zerstörungsfreier Sauerstoffanalysen am Forschungsreaktor München erlaubt, wird beschrieben. Die Aktivierung durch thermische Neutronen wurde durch Einbau eines Cadmiumschildes am Bestrahlungsort unterdrückt. Sauerstoffanalysen wurden in Gegenwart zahlreicher Matrixelemente durchgeführt, um zu ermitteln, welche Elemente die aktivierungsanalytische Sauerstoffbestimmung mit schnellen Reaktorneutronen erschweren oder unmöglich machen.Wir danken der Betriebsleitung und der Bestrahlungsgruppe des FRM für deren verständnisvolles Eingehen auf unsere Wünsche, Herrn Dr. Köhler für seine wertvollen Hinweise beim Aufbau der schnellen Rohrpost und Herrn E. Pfeffermann für seine Mithilfe bei einem Teil der Messungen.