Untersuchungen in der Reihe der Methyl-1,2-benzanthrachinone

Ohne Zusammenfassung1. MitteilungVorgelegt in der Sitzung am B. Juli 1911     

Intramolekulare Cycloadditionen in der Reihe der Binaphthyle

Intramolecular cyloadditions of binaphtyl compounds Three new bridged ketones, 7,8 and 9 , have been isolated in 44%, 3% and 19% yields respectively (Scheme 2) by heating 2,2′-bis-allyloxy-1,1′-binaphthyl ( 5 ) at 215° for 16 hours. These compounds could be epimerized about C(16) by bases, and in particular 9 yielded the new epimer 10 . The structures of the alcohols obtained by reduction of the keto group are also given (Scheme 2). The constitution of all compounds was derived from spectroscopic data, chiefly from their ¹H-NMR, spectra (tab. 2, 3 and fig. 1). The assignments were based on the observed long-range coupling constant between H(endo)-C(16) and H(endo)-C(5) in 7 and 10 and on the analysis of chemical shifts and coupling constants in both the ketones and their derivatives. Moreover, the structures of the compounds investigated have been proved by x-ray analysis of ketone 8 (chap. 3, fig. 2). The thermal conversion of binaphthylether 5 to the bridged ketones proceeds via an intramolecular Diels-Alder reaction, followed by Claisen rearrangement (Scheme 8). On heating, the bis-beta-methylallyl ether 20 yielded the ketone 21 and a small amount of the ether 23 (Schemes 5 and 7). Ether 23 and binaphthyl monoallyl ether 26 were converted thermally to the bridged ketones 31 (Scheme 7) and 27 (Scheme 6) respectively. In addition, 26 underwent an intramolecular ene-reaction to give the spiroketone 28 (Schemes 6 and 9). The structures of these compounds were also established, mainly by analysis of their ¹H-NMR. spectra.     

Konformative Beweglichkeit Flexibler Ringsysteme–XI Untersuchungen mit Hilfe der Protonenresonanzspektroskopie Ringinversion bei Methyl- und Alkoxylcyclohexanen

The ring inversion of cyclohexane derivatives with one, two and three pairs of geminal methyl and alkoxyl groups has been studied by investigations of the temperature dependence of the NMR signals. The rate of the inversion depends on the number and the relative positions of the ligand pairs as well as on their size. A single pair of geminal ligands has only a very slight effect on the inversion rate. Two ligand pairs hinder the inversion when they are in the 1 and 4 positions relative to one another, but facilitate it when they are in the 1 and 3 positions. In both cases the effects are smaller with methoxyl groups than with methyl groups. Three ligand pairs significantly increase the inversion rate when they are in the 1, 3 and 5 positions, but reduce it when they are in the 1, 2 and 4 positions. The effect of 1,3 substituents is attributed to an increase in the energy of the ground state of the molecules whereas the effect of 1,4 arranged substituents is attributed to an increase in the energy of the transition state of the chair inversion.     

Synthesestudien in der Reihe der Aza-azulene. I

Zusammenfassung Es wird die Synthese des Dekahydro-7-aza-azulens und des Dekahydro-7-aza-vetivazulens beschrieben. Der stickstoffhaltige Sieben-Ring wurde durchBeckmannsche Umlagerung des entsprechenden Oxims und nachherige Reduktion des Laktames mit Lithiumaluminiumhydrid erhalten.     

Inversion der Antischaumf?higkeit in der Reihe der Fettalkohole

Ohne Zusammenfassung     

Zur numerischen Festlegung der lyotropen Reihe der einwertigen Kationen

Zusammenfassung Es wird eine Methode angegeben, welche auf Grund von Flockungsversuchen lyophober Sole die numerische Festlegung der lyotropen Reihe erm?glicht. Vorl?ufige Mitteilung: Büchner, Voet und Bruins, Proc. Acad. Sci. Amsterdam35, 563 (1932).     

Untersuchungen der Teilsysteme: Aluminium-TiSi2, -ZrSi2, -MoSi2 und -WSi2

Ohne ZusammenfassungHerrn Professor Dr.F. Wessely zum 60. Geburtstage in aufrichtiger Verehrung zugeeignet.     

Untersuchungen der Fluoro-metallate(III), 2. Mitt.: Thermoanalytische Untersuchungen von Hydrazinium-(1+ und2+)-fluoro-aluminaten-gallaten,und-indaten

Zusammenfassung Die thermische Zersetzung dieser Verbindungen im Argon wird beschrieben und führt zu den drei neuen Verbindungen N₂H₅GaF₄, N₂H₅InF₄ und N₂H₅GaF₄·N₂H₆F₂. Außerdem sind zwei neue Phasen mit den Verhältnissen N₂H₄2 Ga6 F und N₂H₄In3F isolierbar. Die thermische Zersetzung von N₂H₆AlF₅ verläuft analog dem N₂H₆GaF₅ ohne trennbare Stufen. Gitterabstände und IR-Spektren der neuisolierten Phasen sind angegeben.

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Fluoro metallates(III), II: Thermoanalytical investigation of hydrazinium(¹⁺ and²⁺)-fluoroaluminates,-gallates, and-indates

The thermal decomposition of these compounds in argon results in the following three new compounds: N₂H₅GaF₄, N₂H₅InF₄, and N₂H₅GaF₄·N₂H₆F₂. Besides, two new phases with composition N₂H₄2 Ga6 F and N₂H₄In3 F are noticed. The thermal decomposition of N₂H₆AlF₅ follows the same path as N₂H₆GaF₅, but no separable steps could be observed. IR spectra together with the d spacings of the new compounds are included.

     

Zum Nachweis von Aminen der aromatischen Reihe

Ohne Zusammenfassung     

Ba2NiTeO6 – eine neue Verbindung in der Reihe der hexagonalen Perowskite

Ba₂NiTeO₆ — a novel compound in the series of hexagonal perovskites (Ba₂)(¹²)(NiTe)(⁶)O₆ crystallizes in the rhombohedral space group R3 m with a = 5.797 and c = 28.595 Å for the unit cell in the trigonal setting, which contains 6 formula units. The crystal structure was solved by single crystal X-ray diffraction and refined down to R = 2.9%. It can be described by 12 close-packed BaO₃ layers alternating in the sequence hhcchhcc…, with an ordered occupation of the octahedral lattice sites by Ni and Te atoms. Groups of three octahedra, which are connected with one another by common faces, are linked with each other by TeO₆ octahedra via common corners. The central octahedra of these face-linked groups are occupied by Te, the outer ones by Ni. The bonding within the NiO₆ polyhedra is discussed on the basis of the ligand field spectra and compared to similar compounds. It is shown that there can be an appreciable change of the ligand field parameter Δ (30%) even when the Ni — O distances are nearly equal — in contrast to the predictions of the crystal field theory. Effects of this kind are observed under certain structural conditions, when the bonding within the NiO₆ polyhedra is changed indirectly by substitution of atoms with a noble gas configuration (W⁶⁺) by atoms with a d¹⁰-configuration (Te⁶⁺) in the cationic environment of Ni²⁺.     

Synthese eines homologen steroidischen 17β-Pyrrolinons Partialsynthetische Versuche in der Reihe der Herzgifte, 9. Mitteilung

Synthesis of a homologous steroidal 17β-pyrrolinone. We describe the synthesis of 4′-[(3β-Hydroxy-androst-5-en-17β-yl)methyl]-3′-pyrrolin-2′-one ( 15 ) starting from 3β-acetoxy-23-diazo-21,24-dinorchol-6-en-22-one ( 1 ).