Herstellung keramischer Pulver. III [1]: Über die Struktur diamagnetischer Titan(III)-alkoxide

Inhaltsübersicht. Es wird über die Darstellung der Verbindung Ti(OCH₂CH₂OC₂H₅)₃ berichtet. Diamagnetismus und VIS-NIR-Absorptionsspektrum weisen auf eine ungewöhnliche Struktur hin. Semiempirische MO-Berechnungen (EHT) an ausgewählten Koordinationspolyedern ergeben für die Struktur eines flächenverknüpften Doppelwürfels qualitative Übereinstimmung mit den experimentellen Befunden. Preparation of Ceramic Powders. III. About the Structure of Diamagnetic Titan (III) Alkoxides The preparation of the compound Ti(OCH₂CH₂OC₂H₅)₃ is reported. Diamagnetism and absorption spectrum indicate an unusual structure. The results of semiempirical MO computations (EHT) for selected coordination polyhedra agree qualitatively with the experimental data for a double-cube structure of the compound.     

Herstellung keramischer Pulver. IX. Zur Bildung von NiMn2 O4 und ZnMn2O4 durch Zersetzung von [Ni(H2O)6] (MnO4)2 und [Zn(H2O)6] (MnO4)2

Preparation of Ceramic Powders. IX. NiMn₂O₄ and ZnMn₂O₄ Formation by Decomposition of [Ni(H₂O)₆] (MnO₄)₂ and [Zn(H₂O)₆] (MnO₄)₂ Improved preparation of Ba(MnO₄)₂ from BaMnO₄ is reported. Thermal or hydrothermal decomposition of [Ni(H₂O)₆] (MnO₄)₂ yields intermediately an amorphous manganate(IV) which forms crystalline NiMnO₃ and α-Mn₂O₃ in the range T > 400°C. NiMn₂O₄ is formed above 730°C in accordance with the phase diagram. On the other hand, ZnMn₂O₄ is already at 300°C obtained from [Zn(H₂O)₆](MnO₄)₂ at hydrothermal conditions.     

Über die Bildung von Phosphor(III)-oxychlorid,POCl, durch Pyrolyse von Allyldichlorphosphit. Massenspektroskopische und Matrix-Infrarot-Untersuchungen

On the Formation of Phosphorus(III) Oxychloride, POCl, in the Pyrolysis of Allyl Dichlorophosphite. Mass Spectroscopic and Matrix Infrared Studies Phosphorus(III) oxychloride, previously prepared via different routes, is formed in the pyrolysis of allyl dichlorophosphite at 1150 K. The compound was characterized by mass spectroscopic and matrix infrared methods.     

Über Erdalkalimetalloxothallate. II. Darstellung und Kristallstruktur von Ba2Tl2O5

On Alkaline Earth Metal Oxothallates. II. Preparation and Crystal Structure of Ba₂Tl₂O₅ Ba₂Tl₂O₅ was prepared and investigated by X-ray single crystal methods (space group D? Pcmn, a = 6.264, b = 17.258, c = 6.05 Å) Ba₂Tl₂O₅ is isotypic with Ca₂Fe₂O₅.     

Anil-Synthese 18. Mitteilung. Über die Herstellung von Styryl-Derivaten des 3-Phenyl-benzisoxazols

Preparation of styryl derivatives of 3-phenyl-benzisoxazole 3-(p-Tolyl)-1,2-or 2, 1-benzisoxazoles and 6-methyl-3-phenyl-1,2-benzisoxazoles react with anils of aromatic aldehydes in the presence of dimethylformamide and potassium hydroxide or potassium t-butoxide to yield the corresponding 3-(stilben-4-yl)-1,2- or 2,1-benzisoxazoles and the 3-phenyl-6-styryl-1,2-benzisoxazoles respectively (‘Anil Synthesis’). Further, the Schiff's bases derived form chloroanilines and 3-(p-formylphenyl)-1,2-benzisoxazoles yield, with methyl-and p-tolyl substituted heterocyles the corresponding heterocyclic substitued styryl and stilbenyl derivatives.     

Anil-Synthese. 23. Mitteilung. Über die Herstellung von Styryl- und Stilbenyl-Derivaten des Pyrimidins

Preparation of Styryl and Stilbenyl Derivatives of Pyrimidines 2- and 4-(p-Tolyl)-substituted pyrimidines react with anils of hetero-aromatic aldehydes in the presence of dimethylformamide and potassium hydroxide or potassium t-butoxide to yield the corresponding 2- and 4-[4″-(heteroaryl)stilben-4′-yl]pyrimidines or the 2- and 4-[a-(heteroaryl)-4′-styryl]pyrimidines respectively (‘Anil synthesis’). Furthermore, the Schiff′s bases derived from p-chloroaniline and 4-(pyrimidine-2-yl and 4-yl)benzaldehydes give, with methyl- and with p-tolyl-substituted heterocycles, the corresponding heterocyclic substituted styryl and stilbenyl derivatives. Alkyl-, alkoxy- or phenyl-substituted pyrimidines undergo also the ‘Anil synthesis’.     

Über die Reaktion von W3O mit lod. Darstellung,Kristallstruktur und Eigenschaften von WOI3

On the Reaction of W₃O with Iodine: Preparation, Crystal Structure, and Properties of WOI₃ The novel tungsten oxide iodide WOI₃ is obtained from the reaction of the metalrich tungsten oxide W₃O (also known as ‘β-tungsten’) with iodine in a sealed glass tube placed in a temperature gradient (440–400°C). In the low-temperature region WOI₃ is formed as mouse-grey intergrown needle-like crystals. WOI₃ crystallizes in the tetragonal NbOCl₃ structure type, space group P4₂/mnm, with a = 12.346(2), c = 3.765(1) Å (20°C). The crystal structure at – 130°C was determined from single-crystal diffractometer data (R = 0.023). Results of magnetic susceptibility and vibrational spectroscopic measurements are given together with the mass spectrum of WOI₃ obtained on heating.     

Über Chalkogenolate. 132. Untersuchungen über Rhodanine 3. Darstellung und Charakterisierung von Thiorhodanin und 5-Methylthiorhodanin. Versuche zur Herstellung von Trithiopyruvinsäure

On Chalcogenolates. 132. Studies on Rhodanines. 3. Synthesis and Characterization of Thiorhodanine and 5-Methyl Thiorhodanine. Attempts to Prepare Trithiopyruvic Acid The reactions of rhodanine and 5-methyl rhodanine with P₄S₁₀ and with Lawesson reagent yield the title compounds, which have been characterized with electron absorption, ¹H and ¹³C NMR, infrared, and mass spectra. Attempts to synthesize trithiopyruvic acid by use of different procedures were not successful.     

Über einige Umwandlungsprodukte des «BLIX-Sulfatids» und die Herstellung von quartären Dihydro-sphingosinium-Salzen

In the sulfatide fraction of beef spinal-cord, isolated according to the method of BLIX [9] and LEES [14], there are also sulfatides present derived from 2S, 3R-1, 3-dihydroxy-2-amino-octadecane.     

Über die Deammonisierung und Dehydroxylierung von NH4-Chabasit

Deammoniation and Dehydrosylation of NH₄-Chabazite The deammoniation of NH₄-chabazite is completely reversible. Compared to other investigated zeolites the hydrogen form of chabazite remains stable at higher temperatures and over a wider temperature range. Thermoanalytic and by IR spectrophotometry two types of OH groups with OH-stretching bands at 3565 and 3615 cm^?1 can be distinguished. Water saturation of H-chabazite at room temperature results in irreversible changes of the crystal structure. The thermostability of the deriving lattice is extremely low and no acidic OH groups are detectable any more. It is supposed that in the completely hydrated H-chabazite acidic H₃O⁺ ions solved out aluminium from the lattice which occupies some of the cationic lattice sites. The dehydroxylation is an irreversible process and is accompanied by a lattice collapse.     

Über die Bildung von röntgenamorphem Eisen(III)-hydroxid durch Luftoxydation von Eisen(II)-hydroxid und Eisen(II)-carbonat

In the presence of certain foreign cations (Ca²⁺, Mg²⁺), amorphous iron(III) hydroxide may be obtained from Fe^II hydroxide or carbonate by air oxidation.     

Über die Bildung der Jodphosphine PH2J und PHJ2 aus Phosphin und PJ3, P2J4 bzw. J2

The iodophosphines PH₂J and PHJ₂ are formed by the reaction of PH₃ with PJ₃, P₂J₄ or J₂ respectively. They are stable only in equilibria mixtures together with PH₃, PJ₃ and P₂J₄ in the presence of HJ. H-NMR-spectra: PHJ₂ doublett ?5,03 ppm, J_{P? H} = 145 Hz, PH₂J doublett ?2,95 ppm, J_{P? H} = 168 Hz. P-NMR spectra: PHJ₂ doublett +9 ppm, J_{P? H} = 145 Hz, PH₂J triplett +156 ppm, J_{P? H} = 168 Hz. The IR-spectra of PH₂J and PHJ₂ are reported.     

Über die Reaktion von Schwefel mit Aminen und Formaldehyd. Eine neue Methode zur Herstellung von Thioformamiden und Dithiocarbamaten

The reaction of sulfur with primary or secondary amines and formaldehyde has been studied. A simple one step process for the preparation of thioformamides (RR′NCHS; R ? H, R′ ? CH₃, C₂H₅; R ? R′ ? CH₃, C₂H₅; R+R′ ? ? (CH₂), ? (CH₂), ? C₂H₄OC₂H) and the amine salts of N, N-dialkyl-dithiocarbamic acids (R₂NCS₂ · H₂NR₂, R ? CH₃, C₂H₅, C₄H₉; R₂ ? ? (CH₂), ? (CH₂), ? C₂H₄OC₂H) is reported. In addition, the isolation of diethylamidosulfoxylic acid, (C₂H₅)₂NSOH · 1/2 H₂O, the first derivative of a new class of compounds, is described. The physical properties and the ¹H-NMR. spectra of the above mentioned compounds are given.     

Über die Synthese von Erdalkalimetalldihalogeniden und die Strukturen von Ca3Br2CBN und Sr3Cl2CBN

On the Synthesis of Alkaline-Earth Dihalides and the Structures of Ca₃Br₂CBN and Sr₃Cl₂CBN The reaction of alkaline-earth carbonates with ammonium chloride or bromide yields alkaline-earth dihalides at relatively low temperatures (300°C). Ca₃Br₂CBN and Sr₃Cl₂CBN were synthesized in sealed niobium containers at 950°C from the metal, its dihalide, boron nitride and graphite. The crystal structure of Sr₃Cl₂CBN was refined from single crystal data. Sr₃Cl₂CBN crystallizes isotypic with Ca₃Cl₂CBN in the orthorhombic space group Pnma (No. 62) with a = 1448.4(2) pm b = 405.46(5) pm, c = 1170.0(1) pm. The lattice constants of Ca₃Br₂CBN and Sr₃Cl₂CBN were determined by orthorhombic indexing of the powder patterns (Ca₃Br₂CBN: a = 1444.3(2) pm, b = 390.64(6) pm, c = 1139.2(2) pm; Sr₃Cl₂CBN: a = 1444.0(4) pm, b = 405.27(8) pm, c = 1167.8(2) pm). There was no success in preparing homologues with Barium.     

Über die Reaktion von HCl im System HF/SbF5 und die Kristallstruktur von SbCl3F2

On the Reaction of HCl with HF/SbF₅ and the Crystal Structure of SbCl₃F₂ The reaction of HCl in HF/SbF₅ solution at ?78°C yields H₂F⁺SbClF₅^?. At ?40°C formation of SbCl₃F₂ was observed, which crystallizes in the tetragonal space group I-4 with a = 1 281.6(5) pm, c = 758.1(6) pm with 8 formula units per unit cell. The structure contains cis-fluorine-bridged tetramers, in which Sb has a distorted octahedral coordination.